Conferência Sobre Espectroscopia Raman

Program and Abstract Volume
LUNARAND
PLANETARY
INSTITUTE LPI Contribution No. 1473
Conference on
Micro-Raman Spectroscopy and Luminescence
Studies in the Earth and Planetary Sciences
April 2-4, 2009 • Mainz, Germany
Sponsors
Max-Planck-Gesellschaft
(Max-Planck-Institute fUr Chemie)
Lunar and Planetary Institute
Hosted by
Max-Planck-Institute fUr Chemie, Abteilung Geochemie
Conveners
Arnold Gucsik
Max-Planck-Institut fiir Chemie,
Abteilung Geochemie, Mainz, Gennany
Jens G6lze
TV Bergakademie Freiberg,
Institut fUr Mineralogie, Freiberg, Gennany
Local Organizing Committee

Rosemarie Gross
Max-Planck-Institut fUr Chemie
Arnold Gucsik
Ulrich Ott
Lunar and Planetary Institute 3600 Bay Area Boulevard Houston TX 77058-1113
LPI Contribution No. 1473

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Preface
This volume contains abstracts that have been accepted for presentation at the Conference on
Micro-Raman Spectroscopy and Luminescence Studies in the Earth and Planetary Sciences,
April 2~, 2009, Mainz, Germany.
Administration and publications support for this meeting were provided by the staff of the
Publications and Program Services Department at the Lunar and Planetary Institute.
Conference on Micro-Raman Spectroscopy and Luminescence Studies v
Contents
Program 1
Application of Cathodoluminescence to Recognize Diagenetic Trends of Carbonate Rocks

R. Abbasi, M. H Adabi, and M. Moradpour 9
Ca-poor Pyroxine Raman Characteristics in H Ordinary Chondrites

L. A. Alba-Aldave, K. E. Cervantes-de la Cruz, R. Y Sato-Berru. C. Linares-Lopez,
M. A. Reyes-Salas, and F. Ortega-Gutierrez 10
Micro-Raman Determination of the Composition ofUgrandite Garnets

D. Bersani, S. Ando, P. Vignola, I-G. Marino, and P. P. Lottici 12
Micro-Raman Spectroscopy and Electron Microscopy of Shock Veins in Metaquartzites from the
Vredefort Impact Structure: Controls on Coesite and Stishovite Genesis
S. Boonsue and J Spray 13
Raman Spectra of a Fine-grained Labradorite Sample Heated to Typical

Mercury Dayside Temperatures
U. BOttger, J Helbert, A. Maturilli, and H-W Hubers 15
Characterization hy Cathodoluminescence Spectroscopy of Silica Phases as Indicator of the

Shock in Meteorites
H Chennaoui A oudjehane, A. Jambon, 0. Boudouma, and B. Reynard 17
Spectrally-resolved Thermoluminescence on Hydrothennal Aragonite

E. Crespo-Feo,1. Garcia-Guinea, r Correcher, and A. Garralon 18
LuCIDD: A Luminescence Instrument with Confocal and Imaging Units for

Dating and Dosimetry
R. DeWitt and D. M. Klein 20
Dating the Light Shielded Surface of Cobbles to Reconstruct Past Sea Levels in Antarctica
R. DeWitt, P. Kouremenos, A. M. Drewry, and A. R. Simms 22
ODIN: A Prototype Miniature Luminescence Instrument for Dating of Martian Regolith

R. DeWitt, S. W S. McKeever, M. W Blair, and D. K. Reust 24
Confocal Raman Imaging in Geosciences

T Dieing, A. Jauss. U. Schmidt, andJ Toporski 26
Impulse Cathodoluminescence Silicate Glasses

V. E. Eremyashev 27
Investigating the Oldest Traces of Life by AFMlConfocal Raman Spectroscopy:

Applications for the Analysis of Martian Rocks
F. Foucher and F. Westall 28
Gated Laser-based Spectroscopy of Minerals: Luminescence, Raman, LIBS

M. Gaft 30
Spectrally-resolved Luminescence of Moganite from Mogan (Gran Canaria)

J Garcia-Guinea, M. A. Bustillo, E. Crespo-Feo, A. A. Finch, P. D. Townsend,
D. E. Hole, and V. Correcher 32
vi LPI Contribution No. 1473
The Quartzofeldspathic Fulgurite ofBustarviejo (Madrid): Glassy Matrix and Silicon Phases
1. Garcia-Guinea, M. Furia, M Fernandez-Hernan, M. A. Bustillo, E Crespo-Feo,
V. Correcher, L. Sanchez-Munoz, and E. Matesanz 34
Spectra Cathodoluminescence and Raman Imaging ofNa-rich Feldspar and Maskelynite from the
Villalbeto de la Pena Meteorite
J. Garcia-Guinea, L. Sanchez-Munoz, L. Torma, E. Crespo-Feo,1. Ruiz,
A. 1. Marlin-Herrero, and A. Cremades 36
Cathodoluminescence of Lunar Minerals and Rocks

J. GOtze 38
Cathodoluminescence Microscopy and Spectroscopy of Shocked Zircon from the

Vredefort Impact Structure, South Africa
A. Guesik 40
Scanning Electron Microscope-Cathodoluminescence and Micro-Raman Properties of

Kaba CV3 Chondrite
A. Guesik, Sz. Berezi, T. Okumura, H. Nishido, K. Ninagawa, and Sz. Nagy .42
Cathodoluminescence Characterization ofNanodiamonds: An Application to the

Meteoritic anodiamonds
A. Guesik, H. Nishido, T. Nakazato, and K. Ninagawa .44
Thermo-Luminescence Glow Curves and Photoluminescence afton Irradiated AhO)

K. S. Jheeta 45
Micro-Raman Spectroscopy of Diamonds from JaH 054 and Sahara 98505 Ureilites,
Statistic Research
A. Karezemska, T. Jakubowski, M Kozaneeki, M Szurgot, A. Guesik, and S. Mitura 47
Cathodoluminescence and Raman Spectroscopic Characterization of Experimentally

Shocked Plagioclase
M Koyama, A. Guesik, H. Nishido, K. Ninagawa, and A. Tsuehiyama .49
Cathodoluminescence Characterization of Maskelynite and Alkali Feldspar in Shergottite

M Kayama, T. Nakazato, H. Nishido, K. Ninagawa, and A. Gucsik 50
Cathodoluminescence of Shocked Plagioclase and Alkali Feldspar from Ries Crater, Germany
M Kayama, H. Nishido, K. Ninagawa, and A. Guesik 51
Confocal Raman Imaging of Fluid Inclusions in Garnet from Diamond-Grade Metamorphic Rocks
(Kokchetav Massif, ortbern Kazakhstan)
A. V. Korsakov, T. Dieing, A. V. Golovin, and 1. Toporski 52
MoonShot: A Combined RamanlLffiS Instrument fnr Lunar Exploration

E. C. Laan, W. van Westrenen, A. Wielders, M 1. Heiligers, and the MoonShot Parlners 54
The IR Emission of the Mixed Ices (NH,+H20+CH,OH) Induced by IS keY H,· Ion
C. S. Lee, W. lp, C. N Chou, and C. W. Hwang 55
CL Study of the Low-Grade Feldspar Alteration

1. Leiehmann and l Broska 56
Conference on Micro-Raman Spectroscopy and Luminescence Studies vii
Decoding Environmental Conditions During Silicification of Plant Stems in Equatorial Pangaea

and Oman by Cathodoluminescence Imaging and Analysis
P. Malysowi, 1. Golze, G. Forbes, 1. I.eiehmann, R. Roftler, and T Grygar 57
Cathodoluminescent Features and Raman Spectroscopy of Miocene Hydrothennal

Biomineralization Embedded in Cryptocrystalline Silica Varieties, Central Europe, Hungary
A. Muller, M. Polgari, A. Guesik, Sz. Nagy, M Veres, E Pal-Molnar, 1. Golze,
C CserhQti, T Nemeth, and M. Hamor-Vid6 59
Evidence of Shock Metamorphism in Hungarian L-Chondrites Using Raman Spectroscopy

Sz. Nagy, A. Guesik, Sz. Berezi, M. Veres,1. Gyollai, and 1. Fur) 61
Thennoluminescence Study of Ordinary Chondrites

K. Ninagawa 63
Cathodoluminescence Microcharacterization of Ballen Silica in Impactites

T Okumura, A. Cuesik, H. Nishido, and K. Ninagawa 65
Spectral and Microscopic Analyses of Fossil Microorganisms in a Jurassic Oolitic Limestone

Y Rubert, C Ramboz, P. Gautret, T Dieing. F Westall, D. Bonijoly,
Y M. I.e Nindre, and C. Lerouge 66
In-Situ Micro·Raman and Moessbauer Spectroscopic Study of Evaporate Minerals in

Rio Tinto (Spain): Applications for Planetary Exploration
F Rull, G. Klingelhofer, A. Sansano, I. Fleileher, P. Sobr6n, M. Blumers, A. Lafuente,
D. Sehmonke, and 1. Maul 68
Mineral Characterization of Silicified Coral from \Vestem Sumatra, Indonesia

1. Sanchez-Munoz, M. A. Bustillo, 1. Goreia-Guinea, E Crespo-Feo, and 1. Tormo 70
Cathodoluminescence (CL) Studies ofUHP-Metamorphic Rocks from Dora MairalWestem Alps:

Petrological Applications and High Resolution Spectroscopy
H P. Scherll, T Galle, R. D. Neuser, and D. K. Richter 72
Uncommon Calcite Crystals in Cambrian and Ordovician Limestones from Onshore and Offshore
Northern Poland - Evidence from Cathodoluminescence
M. Sikorsko : 73
Order-Disorder in K-Feldspar Grown from Mixed Magmas - CL and Raman Study

E Slaby, 1. Gotze, G. Worner, K. Simon, R. Wrzalik, and M. Smigielski 75
Raman Spectroscopy, a Powerful Tool for the Characterization of Hydrated Sulfates and
Acidic Water in Rio Tinto (Spain)
P. Sobron, A. Sansano, A. Sanz, T Acosta, B. Lafuente, F. Rull, F. Sobron, and 1. Medina 77
Identification of Minerals in DaG 610 and in NWA 869 Meteorites by Micro-Raman Spectroscopy
M. Szurgot, A. Karezemska, M. Kozaneeki, T Jakubowski, and S. Milura 79
Micro-Raman Spectroscopy ofNWA 4047 Meteorite

M. Szurgot, K. Kisiel, and R. Kisiel 81
Comparative Raman Study of Different Mars Analog Materials

N. Tareea, M. Hilehenbaeh, W Goetz, H Steininger, and 1. Popp 83
viii LPI Contribution No. 1473
The Cali Meteorite: Luminescence of a Recently Fallen HIL Ordinary Chondrite

1. M Trigo-Rodriguez, 1. Llorca, and D. W G. Sears 85
Photoluminescence Study of Hydrogen-rich Gray-to-Blue-to-Violet Diamonds from the

Argyle Mine, Australia
C. H. van der Bogert, C. P. Smith, T. Hainsehwang, and S. F. McClure 87
Pathways and Rates ofMg-Sulfate Dehydration and Rehydration on Mars

A. Wang and 1. 1. Freeman 89
Behaviour of Vitroceramics for Nuclear Waste Storage Probed by Raman and Luninescence
G. Panezer, C. Mendoza, and D. de Ligny 91
Conference on Micro·Raman Spectroscopy and Luminescence Studies
Program
Thursday, April 2, 2009
Opening Remarks
8:45 a.m.
8:45 a.m. Gucsik A.·

Opening Remarks and Welcome
9:00 a.m. Gaf! M. * [INVITED]

Gated Laser-based Spectroscopy ofMinerals: Luminescence, Raman, LIBS [#3041]
9:45 a.m. BREAK
MICRO-RAMAN STUDIES OF TERRESTRIAL MATERIALS

10:10 a.m.
Chairs: Michael Galt

Andrey Korsakov
10:10 a.m. Tareea N. * Hilchenbaeh M. Goetz W. Steininger H. Popp J.

Comparative Raman Study ofDifferent Mars Analog Materials [#3022]
10:30 a.m. Bersani D. * Andil S. Vignola P. Marino I.-G. Lottiei P. P.

Micro-Raman Determination ofthe Composition ofUgrandite Garnets [#30371
10:50 a.m. Korsakov A. V. * Dieing T. Golovin A. V. Toporski J.

Confocal Raman Imaging ofFluid Inclusions in Garnet from Diamond-Grade Metamorphic Rocks
(Kok1:hetav Massif, Northern Kazakhstan) [#30431
11: 10 a.m. Dieing T. * Jauss A. Schmidt U. Toporski J.

Confocal Raman Imaging in Geosciences [#30451
II :30 a.m. Panezer G. * Mendoza C. de Ligny D.

Behaviour of Vitroceramics for Nuclear Waste Storage Probed by Raman and Luninescence [#30511
11 :50 a.m. LUNCH

2 LPI Contribution No. 1473

MIRCO-RAMAN INVESTIGATIONS OF EXTRATERRESTRIAL MATERIALS
1:30 p.m.
Chairs: Alian Wang

Arnold Guesik
I:30 p.m. Foucher F.' Westall F.

Investigating the Oldest Traces ofLife by AFMlConfoca/ Raman Spectroscopy: Applications for the
Ana/ysis ofMartian Rocks 1#3007J
1:50 p.m. Laan E. C.' van Westrenen W. Wielders A. Heiligers M. J. MoonShot Partners
MoonShot: A Combined Raman/LIES Instrument for Lunar Exp/oration 1#3021)
2:10 p.m. Karczemska A.' Jakubowski T. Kozanecki M. Szurgot M. Gucsik A. Mirura S.

Micro-Raman Spectroscopy ofDiamonds from JaH 054 and Sahara 98505 Ureilites.
Statistic Research 1#3025)
2:30 p.m. Wang A.' Freeman J. J.

Pathways and Rates ofMg-Suifate Dehydration and Rehydration on Mars 1#30341
2:50 p.m. BREAK

Conference on Micro-Raman Speclroscopy and Luminescence Swdies 3

CHARACTERIZAnON OF SHOCK METAMORPHISM
BY CL AND MICRO-RAMAN TECHNIQUES
3:10 p.m.
Chairs: Suporn Boonsue

Masahiro Kayama
3:10 p.m. Nagy Sz.· Gucsik A. Berczi Sz. Veres M. Gyollai I. FOrj J.
Evidence ofShock Metamorphism in Hungarian L-Chondrites Using Raman Spectroscopy 1#3012)
3:30 p.m. Kayama M.· Gucsik A. Nishido H. Ninagawa K. Tsuchiyama A.

Cathodoluminescence and Raman Spectroscopic Characterization ofExperimentally
Shocked Plagioclase 1#3017)
3:50 p.m. Boonsue S.· Spray J.

Micro-Raman Spectroscopy and Electron Microscopy o/Shock Veins in Metaquartzites/rom the
Vredefort Impact Structure: Controls on Coesite and Stishovite Genesis 1#30351
4: 10 p.m. Gucsik A.•

Cathodoluminescence Microscopy and Spectroscopy ofShocked Zircon from the Vredefort Imapct
Structure, South Africa 1#30421

POSTER SESSION
4:30 p.m.
SikorskaM.
Uncommon Calcite Crystals in Cambrian and Ordovician Limestones from Onshore and Offshore
Northern Poland - Evidence from Cathodoluminescence [#3002[
Garcia-Guinea 1. Bustillo M. A. Crespo-Feo E. Finch A. A. Townsend P. D. Hole D. E. Correcher V.

Spectrally-resolved Luminescence ofMoganitefrom Mogan (Gran Canaria) [#3008)
Sanchez-Munoz L. Bustillo M. A. Garcia-Guinea J. Crespo-Feo E. Tormo L.

Mineral Characterization ofSilicified Coralfrom Western Sumatra, Indonesia [#3009]
Crespo-Feo E. Garcia-Guinea J. Correcher V. Garralon A.

Spectrally-resolved Thermoluminescence on Hydrothermal Aragonite [#3010]
Garcia-Guinea 1. Furio M. Fernandez-Heman M. Bustillo M. A. Crespo-Feo E. Correcher V.

Sanchez-Munoz L. Matesanz E.
The Quartzofeldspathic Fulgurite ofBustarviejo (Madrid): Glassy Matrix and Silicon Phases [#3011]
DeWitt R. Klein D. M.
LuCIDO.' A Luminescence Instrument with Confocal and Imaging Units for Dating and Dosimetry [#30301
Garcia-Guinea 1. Sanchez-Munoz L. Tormo L. Crespo-Feo E. Ruiz J. Martin-Herrero A. I. Cremades A.

Spectra Cathodoluminescence and Raman Imaging ofNa-rich Feldspar and Maskelynite from the
Villalbeto de la Pena Meteorite [#3013]
Kayama M. Nakazato T. Nishido H. Ninagawa K. Gucsik A.

Cathodoluminescence Characterization ofMaskelynite and Alkalifeldspar in Shergottite [#3015[
Kayama M. Nishido H. Ninagawa K. Gucsik A.

Cathodoluminescence ofShocked Plagioclase and Alkali Feldspar from Ries Crater, Germany 1#30161
Okumura T. Gucsik A. Nishido H. Ninagawa K.

Cathodoluminescence Microcharacterization ofBallen Silica in Impactites [#30181
Szurgot M. Kisiel K. Kisiel R.

Micro-Raman Spectroscopy ofNWA 4047 Meteorite [#3019]
Alba-Aldave L. A. CelVantes-de la Cruz K. E. Sato-Berru R. Y. Linares-Lopez C.

Reyes-Salas M. A. Ortega-Gutierrez F.
Ca-poor Pyroxine Raman Characteristics in H Ordinary Chondrites [#3033]
Sobron P. Sansano A. Sanz A. Acosta T. Lafuente B. Rull F. Sobron F. Medina J.

Raman Spectroscopy, a Powerful Toolfor the Characterization of Hydrated Sulfates and Acidic Water in
Rio Tinto (Spain) [#3036]
Lee C. S. Ip W. Chou C. N. Hwang C. W.

The IR Emission ofthe Mixed Ices (NH,+H,O+CH,OH) Induced by 15 keV H,' Ion [#3038]
Gucsik A. Berczi Sz. Okumura T. ishido H. Ninagawa K. Nagy Sz.

Scanning Electron Microscope-Cathodoluminescence and Micro-Raman Properties of
Kaba CV3 Chondrite [#3040]
Conference on Micro-Raman Spectroscopy and Luminescence Studies 5
Bottger U. Helbert J. Maturilli A. HUbers H.-W.

Raman Spectra oja Fine-grained Labradorite Sample Heated to Typical Mercury Dayside Temperatures [#3044]
van der Bogert C. H. Smitb C. P. Hainscbwang T. McClure S. F.

Photoluminescence Study ojHydrogen-rich Gray-to-Blue-to- Violet Diamonds from the
Argyle Mine, Australia [#3046J
Szurgot M. Karczemska A. Kozanecki M. Jakubowski T. Mitura S.

Identification oJMinerals in DaG 610 and in NWA 869 Meteorites by Micro-Raman Spectroscopy [#3047]
Friday, April 3, 2009

THERMOLUMINESCENCE AND ITS APPLlCATlO '
TO THE PLANETARY SCIENCES
8:45 a.m.
8:45 a.m. Ninagawa K. * [IJ\'VITED]

Thermoluminescence Study oj Ordinary Chondrites [#3014]
9:30 a.m. BREAK
LUMINESCENCE STUDIES OF TERRESTRIAL MATERIALS

10:00 a.m.
Chairs: Kiyotaka Ninagawa

Jens Goetz
10:00 a.m. Theeta K. S. *

Thermo-Luminescence Glaw Curves and Photoluminescence oJlon Irradiated AI,O, [#30061
10:20 a.m. Leichmann J. * Broska I.

CL Study oJthe Low-Grade Feldspar Alteration 1#30231
10:40 a.m. Schertl H. P. * Gotte T. Neuser R. D. Richter D. K.

Cathodoluminescence (CL) Studies oj UHP-Metamorphic Rocks Jrom Dora Maira/Western Alps:
Petrological Applications and High Resolution Spectroscopy [#3026]
11 :00 a.m. DeWitt R. * Kouremenos P. Drewry A. M. Simms A. R.

Dating the Light Shielded SurJace oJCobbles to Reconstruct Past Sea Levels in Antarctica [#3028]
11 :20 a.m. Abbasi R. * Adabi M. H. Moradpour M.

Application oJCathodoluminescence to Recognize Diagenetic Trends oJCarbonate Rocks 1#3039]
11 :40 a.m. Matysov,; P. * Gotze J. Forbes G. Leichmann J. RoBler R. Grygar T.

Decoding Environmental Conditions During Silicification ofPlant Stems in Equatorial Pangaea and
Oman by Cathodoluminescence Imaging and Analysis 1#30011
12:00 p.m. BREAK

Friday, April 3, 2009

LUMINESCENCE STUDIES OF EXTRATERRESTRIAL MATERIALS
2:00 p.m.
Chairs: Regina DeWitt

Ewa Slaby
2:00 p.m. Gotze J. *

Cathodoluminescence ofLunar Minerals and Rocks [#30041
2:20 p.m. Trigo-Rodriguez J. M. * Llorca J. Sears D. W. G.

The Cali Meteorite: Luminescence ofa Recently Fallen HIL Ordinary Chondrite [#3024J
2:40 p.m. DeWitt R. * McKeever S. W. S. Blair M. W. Reust D. K.

ODIN: A Prototype Miniature Luminescence Instrument for Dating ofMartian Regolith [#30291
3:00 p.m. Gucsik A. * Nishido H. Nakazato T. Ninagawa K.

Cathodoluminescence Characterization ofNanodiamonds: An Application to the
Meteoritic Nanodiamonds [#3048)
3:20 p.m. BREAK

Friday, April 3,2009

RAMAN AND LUMINESCENCE STUDIES
COMBINED WITH OTHER ANALYTICAL TECHNIQUES
3:40 p.m.
Chairs: Marta Polgari

Fernando RuU
3:40 p.m. Slaby E. * Gotze J. Worner G. Simon K. Wrzalik R. Smigielski M.

Order-Disorder in K-Feldspar Grownfrom Mixed Magmas - CL and Raman Study 1#3003]
4:00 p.m. Rull F. * KlingelhOfer G. Sansano A. Fleitcher I. Sobr6n P. Blumers M. Lafuente A.

Schmanke D. Maul J.
In-Situ Micro-Raman and Moessbauer Spectroscopic Study ofEvaporate Minerals in Rio Tinto
(Spain): Applicationsfor Planetary Exploration 1#3027]
4:20 p.m. Muller A. Polgari M. * Gucsik A. Nagy Sz. Veres M. Pal-Molnar E. Gotze J. Cserhati C.
Nemeth T. Hamor-Vid6 M.
Cathodoluminescent Features and Raman Spectroscopy ofMiocene Hydrothermal Biomineralization
Embedded in Cryptocrystalline Silica Varieties, Central Europe, Hungary (#30321
4:40 p.m. Eremyashev V. E. *

Impulse Cathodoluminescence Silicate Glasses 1#3049]
5:00 p.m. Rubert Y. * Ramboz C. Gautret P. Dieing T. Westall F. Bonijoly D.

Le Nindre Y. M. Lerouge C.
Spectral and Microscopic Analyses ofFossil Microorganisms in a Jurassic Oolitic Limestone 1#30501
5:20 p.m. Chennaoui Aoudjehane H. * Jambon A. Boudouma O. Reynard B. [INVITED]

Carcterization by Cathodoluminescence Spectroscopy ofSilica Phases as Indicator ofthe
Shock in Meteorites 1#3031)
6:05 p.m. ROUNDTABLE DISCUSSIONS

Application of Cathodoluminescence to Recognition Diagenetic trends of Carbonate Rocks. R. Abbasi l and

M. H. Adabi' and M. Moradpour' 'School of Earth Science, Shabid Beheshti University, Evin, Velenjak Daneshjo
Blv, Tehran, Iran (r.abbasi@sbu.ac.ir), 'Institute oflranian Oil Company
Introduction: CL images provide insights, not avail-

able by other research techniques, into diagenetic
changes, such as cementation and porosity loss, which
take place in sandstones, shales, and carbonate rocks
during burial[!].
In this study perfonn some cathodoluminescence pic-
tures of Lower Cretaceous (Aptian) Limestones that's
nominate Dariyan Formation is located in southwest of
Iran.
Petrographic and cathodoluminescence observations
suggest diagenetic alteration of Dariyan Formation
occures in a burial setting.
Different generations of sparry calcite cement were
recognized in the Dariyan limestone, ranging from
marine through meteoric to burial cements.
Minescus cement have bright luminescence which
indicates meteoric vadose cement. Poikilotopic sparry
calcite cement is recognized by its very large crystals
with the ability to enclose several grains. Under catho-
doluminescence these cements typically have a dull
luminescence indicating a burial origin.Drusy cements
are meteoric and reveal bright luminescence.Syntaxial
cement is burial too.
Trace elements (Sr, Na, Mn, Fe) bivariates trends and
S18 0 - S"C isotopic plot confirm this idea.[2,3]
photomicrograph of various cement; A) under po-

larizan light are not discriminated cements B) under
cathodoluminescence microscope triple group cements
are recognized, Meteoric minescus cement(white ar-
row) with bright luminescence, Marine cement(pink
arrow) is non luminescence, Burial cement (blue ar-
row) that is dark luminescence
References:
[1] Bogass S. and Krinsely D. (2006) Application of
cathodoluminescence imaging to study of sedimentary
rocks, Cambridge Pub., l65p.[2]Tucker, M.E., and
Wright, V.P. (1990) Carbonate Sedimentology, Oxford
(Blackwell), 482 p.[3]Winefield, P.R., Nelson, C.S.,
and Hodder, A.P.W., (1996). Disriminating temprate
carbonates and their diagenetic environments using
bulk elementalgeochemistry: a reconnaissance study
based on New Zeland Cenozoic limestone: Carbonates
and Evaporites, 11, 19-31.
10 LP! Contribution No. 1473
Ca-POOR PYROXENE RAMA CHARACTERISTIS IN H ORDINARY CHONDRITES, Alba-Aldave Leticia Arace-

Ii', Cervantes-de la Cruz Karina Elizabeth', Sato-Berru Roberto Ysacc' Linares-L6pez Carlos', Reyes-Salas
Margarita Adela!, and Ortega-Gutierrez Fernando!, IInstituto de Geologia, *Universidad Nacional Autonoma de
Mexico, Ciudad Universitaria, Delegacion Coyoacan, Mexico, D.F. c.P. 04510. 2Posgrado en Ciencias de la Tierra,
*.3 Centro de Ciencias y Tecnologia Aplicada, *. 4Instituto de Geofisica, *.
Introduction: Chondrites are meteorites that repre- after each meteorite analyses, the system was cali-
sent the first solids in the early Solar System. Keil and brated to the Raman band of diamond.
Fredrikson [1] provided a chemical classification of Results and discussion: Chondrite H3 spectrum (Fig.
ordinary chondrites based in the content of Fe in oli- I) presents the following main bands: a band near to
vine and in Ca-poor pyroxene, distinguishing 3 241 em", a sharp band at 341 cm-', very small band at
groups: H (high metallic iron), L (low iron) and LL 368 cm-', two broad, composed and asymmetric bands
(low iron-low metal iron) [2,3]. This groups are subdi- at 401 em", and 412 cm-', a weak band at 580 em",
vided according to their petrologic characteristics im- characteristic composed bands at 665 cm-', and 684
printed by the thennal metamorphic processes acting em", finally an intense and symmetric band at 1012
in primitive chondritic materials. Van Schmus and cm"l. When the petrologic type is increased, some dis-
Wood [4] recognized four petrologic types (3, 4, 5 and creet but important differences occurred: Raman spec-
6) of ordinary chondrites. tra of H4 is similar to H3, but in the Raman spectra of
In this work we study the Ca-poor pyroxene Raman H5 and H6, the bands at 368 em" and 412 cm-' disap-
spectra in an H chondrite suite in order to evaluate the pear, while the band at 243 em" has been shifted to
ratio of the polymorphs of these type of pyroxenes. 237 em" and the band at 584 em" to 574 cm-' (Fig. 1).
We chose meteorites with low shock metamorphism
(less than S I) and low weathering degree (less than
AlB). The meteorites with petrologic types 3, 4 and 6
belong to the Antartic Meteorite Collection
(ANSMET) and meteorite type 5 is part of the Mexi-
can Meteoritic Collection of the Universidad Nacional
Autonoma de Mexico. Huang et al. [5] obtained the
r--' IV ','--
A
Raman spectra of several compositions of terrestrial
pyroxenes and proposed that they can be semi- 'Ji- j,'--
quantitatvely determined on the basis of the band posi- ~A
tions of their characteristic Raman modes. In order to
discriminate the Raman data of different petrologic
,
= .. ..
h
Raman shift (ern')
,= ,=
types in the H chondritic series, we used the principal
components analysis (PCA) of the Raman data re- Fig 1.- Raman spectra of the H chondritic suite. Each spectrum is
ported by Sato and collaborators [6]. representative of the different petrologic type obtained with the
Experimental methods: We selected nine enstatite statistical method PeA.
phenocrystals larger than 120 ~m from chondrules and The transformations in H5 and H6 chondrites are
matrix of the meteorites WSG95300 H3.3 [7], due to the phase transition of c1ino-enstatite (Cen) to
GE099102 H4 [8], EET92193 H6 [9] and the type 5 ortho-enstatite (Oen); Ulmer and Stalder[ll] found
Nuevo Mercurio from Mexican National Collection that the differences between Cen and Oen at high pres-
[10]. These crystals were analyzed with a Raman AI- sure and temperature were reflected in the additional
mega XR spectrometer, equipped with an Olympus bands at 369, 431 and 581 cm-' in the Cen spectrum,
(BX51) microscope. Raman spectra were obtained and that the -243 cm-' band shifted to 236 em" in the
with a 532 nm laser of Nd:YV04 and the incident Oen spectrum.
power in the sample was of -10m W. An objective of In the case of meteorite Ca-poor pyroxenes, we
X5D was used for focusing the laser on the sample, found that 368 and 412 cm-' bands disappear in H5
with a spot size of 1.5 ~m. A charge coupled device and H6 chondrites, and that the 412 cm-' band replaced
(CCD), thermoelectrically cooled to -50 'C, is used as the 431 em" band of Ulmer and Stalder Cen spectrum;
a detector to collect the signal in a 180' geometry. The the 584 em" band has been shifted to 574 em" at H5
spectrometer used a grating (675 lines/mm) to resolve and H6, the same as the 237 cm-' band did. The 584
the scattered radiation. Raman spectra were obtained em" band has not disappeared, only has been shifted to
with an exposure time of 500 s. Before, during and a lower frequency at 574 em-I. The main difference
between H5 and H6 spectra are the well defined bands

ofH6.
Perhaps, the 412 cm· l and 574 cm- l anomalous
bands are the main features of low pressure Ca-poor
pyroxenes, and the polymorphic change of Cen to Oen
is reflected in the shifted and dissapeared bands.
One criterion of Van Schmus and Wood [4] classi-
fication to recognized petrologic types is the structure
of enstatite. In the case of petrologic type 3, enstatite is
predominately monoclinic: in type 4 the monoclinic
crystals are abundant «20% voL); in type 5 the pyrox-
ene is orthorhombic with only very minor clinoensta-
tite; and finally in type 6 all the Ca-poor pyroxene is
orthorhombic.
Conclusions: In this work we show that the principal
differences between high pressure and temperature
terrestrial enstatites and low pressure chondritic ensta-
tites are light but important. The polymorphic change
of Cen to Oen can be evaluated by Raman analysis.
Our effort is focussed on the evaluation of the petro-
logic types of ordinary chondrites using the relation-
ship between Cen~Oen polymorphs ratio present in the
different petrologic types.
References:
[I] Keil K. and Fredriksson K. (1964) JGR, 69, 3487-
3515. [2] Prior G.T. (1916) Mineralogical Magazine
18,26-44. [3] Urey H.C. and Craig H. (1953) GCA, 4,
36-82. [4] Van Schmus, W.R., Wood, I.A. (1967)
GCA, 31,747-765. [5] Huang, C.H. Chen, T. Huang,
E.H. Lin, Ii-An Xu. (2000) American Mineralogist,
85,:473-479. [6] Sato Berm RY., Mejia Uriarte E.V.,
Frausto Reyes C., Villagran Muniz M. Murrieta S H.
and Saniger I.M. (2007) Spectrochimica Acta, Part A
,66,557-560. (7] McBride K. and Mason B. (1997).
AMN 30-1,1-20. [8] Satterwhite C. and Mittlefehldt D.
(2001). AMN 24-1, 16. [9] Grossman 1. . (1988). Me-
teorites and the Early Solar System. Edited by Ker-
ridge 1. F. and Mathews M.S. Tucson, Arizona, U.S.A.
University Arizona Press, pp. 6600-679. [10] Fredriks-
son K., Noonan A., Trevino R., Victoria D., Monte-
mayor F., King E.A., Sanchez Rubio G. (1979). Mete-
oritics 15,:93-104. [II] Ulmer P., Stalder R. (2001)
AM 86, 1267-1274.
MICRO-RAMAN DETERMINATION OF THE COMPOSITION OF UGRANDITE GARNETS.

Danilo Bersani 1, Sergio Andel, Pietro Vignola), Iari~Gabriel Marino l and Pier Paolo Lottici l , IDipartimento di Fisi~
ca, Universitil di Parma, Viale G.P. Usberti 7a, 43100 Parma (Italy), 'Dipartimento di Scienze Geologiche e Geotec-
nologie, Universitil di Milano-Bicocca, Piazzale della Scienza 4, 20126 Milano (Italy), 'Consiglio Nazionale delle
Ricerche (CNR), Istituto per la dinamica dei processi ambientali (IDPA), Via Mario Bianco 9, 20131 Milano (Italy).
A fast method to obtain the molar composition of A simple software routine, optimized for the
garnets starting from their Raman spectra was recently ugrandite family, was prepared in order to calculate the
proposed [I]. The method, called MlRAGEM - MIcro- composition of garnets in terms of molar ratio of the
RAman Garnets Evaluation Method - is based on the pure end-members (andradite, grossular and uvarovite)
assumption that in a solid-solution garnet the Raman starting from the frequencies of their main Raman
wavenumbers are linear combinations of end·member bands. The role played by water (hydrogarnets) is dis-
wavenumbers, weighted by their molar fraction. cussed. The results are compared with the composi·
In this work, the application of the MlRAGEM me- tions obtained by means of Wavelength Dispersive
thod to garnets belonging to the ugrandite family is System (WDS) and Energy Dispersive System (EDS)
discussed in detail. The Raman spectra of garnets in electron microprobe measurements, showing very
the andradite-grossular and grossular-uvarovite series good agreement, as visible in the triangular plots re-
are shown in Figs I and 2. ported in Fig. 3.
W05-EMPA 0~, MIRAGEM/"

- \:
'! \\"
, \, '
•",• j' \~,

Andr~.dit" A.
A
A
po,
1'------
A
A""O."
And 0,1 Gro021l
And 0,48 Gro
And 0.18 Gro 0.11
~
MA
0.44~f\-,
t'. .' \:, :i.
-: '.';;--;;-.--;~""10"'' " _-L'
110_ "
Fig. 3: graphical comparison between the composi-
"',
,,".,
~_
GroslOular .J.. GraC.1l3 tions of ugrandite garnets obtained by means of WDS-

.A
I,....,. EMPA and MlRAGEM.
lao 200 SOO 4llO 500 61X1 TOO too t<lO 1000
Some applications in high·resolution provenance
Wavenumber (ern· i )
studies of modern sands and ancient sandstones are
Fig. 1: Raman spectra of gamets in the andradite- shown. This non-destructive and friendly technique
grossular series. can thus be routinely used in petrographic and heavy-
mineral analyses to rapidly determine the distribution
of garnet types and the size-density correlation in dif-
ferent sediment samples.
Grouullr
[I] D. Bersani, S. Andil, P. Vignola, G. Moltiliori,
I.-G. Marino, P. P. Lottici and V. Diella, (2009) Spec-
trochim. Acta A: Mol. Biomol. Spectrosc., do-
i: 10.1016/j.saa.2008.11.033
100 ~o ~ ~ ~ ~ ~ ~ * ~
Wavenumber (em· l )
Fig. 2: Raman spectra of garnets in the grossular-

uvarovite series.
Micro-Raman spectroscopy and electron microscopy of shock veins in metaquartzites from the Vredefort
impact structure: controls on coesite and stishovite genesis
Supom Boonsue and John Spray

Planetary and Space Science Centre, Department of Geology University of New Brunswick, 2 Bailey Drive,
Fredericton, New Brunswick E3B 5A3 Canada (sboonsue@unb.ca,jgs@unb.ca)
Introduction: In this work, we report on the results of a rings, such as quartz, cristobalite, tridymite, and nepheline,
combined scanning electron microscopy and micro-Raman have (T-O-T) vibration bands between 380 and 480 cm-] [1].
spectroscopy investigation of stishovite and coesite in The position of the band at 520-521 crn- l in the Vredefort
shocked Hospital Hill quartzite from the Vredefort impact metaquartzite is consistent with the four member Si04 ring
structure of South Africa. Sanples have investigated using vibration mode ofcoesite. The Raman-shift at 521, 117, 177,
optical microscopy and under the scanning electron micro~ 270, 151,205,355, and 425 cm- l are used for coesite charac·
scope, using energy dispersive x-ray spectrometry (EDS), terization. Typical identification bands for a-quartz are at
and electron back-scattered diffraction (EBSD). Both high- 464, 128, 207 em· l , tbe otber bands at 265, 355, 394, 697,
pressure silica phases were identified by micro-Raman spec- 796, 808, and 1069 are in less intense.
trometery. The conditions of their formation and distribution
related to shock-induced high pressure metamorphism are "In addition to the peak at 521 em-I, it is conspicuous that
discussed in order to better understand the response of plane- quartz bands at 464, 128 and 206 cm- I , with less intense
tary materials to shock metamorphism. spectra at 355 and 425cm-\ are always present in all ana-
lyzed coesite. Based on a number of Raman scans, as well as
Raman mapping, it can be concluded that the principal
quartz band present in all the analyzed coesites is due to the
grain size and phase distribution effects. The micron~ to sub-
micron size of individual crystals and microcrystalline ag-
gregates of coesite relative to the laser spot size, as well as
the partial decay of metastable coesite crystals to quartz are
responsible for the presence of quartz bands in the Raman
spectra of coesite. The SEM images of the microcrystalline
textures confirm this conclusion.
Textural characteristics of coesites occurring in or nearby the

shock vein.
Micro~Rarnan Spectroscopy and Electron Micro-

scopy: Spectra were collected from microcrystalline coesite
aggregates inside quarz grains suspended in the matrix of
-1.5 mm wide shock veins. Raman measurements in the
range of 100-2000 em-I revealed sharp bands with frequen-
cies and relative intensities that were reproducible through-
out the sample. Excitation was achieved using a 514.5-nm
Ar-ion laser, focused through a x50 objective lens Raman spectra of microcrystalline coesite occurring in shock
(N.A=0.75) and filtered to give -8 mW total laser energy at
vein in metaquartzite.
the sample surface. A sample bleaching mode was em-
ployed in the measurement setup to reduce the strong fluo-
The very-high pressure polymorph of 5i0 2, stishovite, occurs
rescence effect from the expoxy mounting glue. The Raman
as submicrometer size «0.5 ).lm) crystals in significantly
spectra of minerals in the shock veins contain well defined
smaller amoWlts than coesite. With a high laser power and a
bands at 463-464,520.897-521, 126-127,204-206 and 269-
long exposure time for spectral aquisition, low intensity Ra-
270 cm· l , whereas groups of less intense bands are found in
man bands at 231, 589 and 753 cm- l can be detected. BSE
the ranges 119-426, 694-800, and 1060-1160 em·'. It has
images reval that the stishovite typically occurs as elongate
been demonstrated that structures with four-member Si04
prisms (needles) in voids close to the edges of metaquartzite
rings, such as coesite and feldspar, have (T-O-T) vibration
ol clasts suspended in the shock vein matrix. Because of its
modes above 500 em , whereas structures with six-member
extremely fine grain size and restricted development, posi- are restricted to shock veins (-1.5 mm wide) and do not oc-
tive identification of stishovite is possible only by the elec- cur in the bulk of the rock. Such P-T excursions are common
tron back-scattered diffraction method. Stishovite, which in in shock veins developed in meteorites [4]. In the Vredefort
crustal rocks is regarded as an indicator of meteorite impact sample, coesite and stishovite also do not occur in the shock
(forming at pressure in excess of 7.5 GPa), was confirmed by vein matrix in the studied sample. Rather they occur within
using Electron Backscatter Diffraction (EBSP). quartzite clasts suspended in the matrix or along the margins
of the shock vein. Stishovite is further restricted to the mar-
gins of clasts and vein walls The shock vein matrix compris-
es microcrystalline quartz and mica., which show indications
of flow textures, set in a brown glassy medium. The matrix-
hosted clasts are rounded and comprise fragments of the host
rock (metaquartzite). The high relief coesite crystals and
microcrystalline aggregates of coesite in the quartzite clasts
are set within a probable diaplectic glass matrix. The radiat-
ing form of microcrystalline coesites around the rim with
quartz concentrated in the centre is common in this rock.
This feature is an indicative of a large volume increase due
to the differences of density between metastable coesite
(density 2.91) and quartz (density 2.65). The coesite, which
is a metastable phase within the stability field of quartz part-
ly transorms to quartz with a consequent volume increase.
The feature is similar to those reported from ultra-high pres-
sure metamorphic rocks [5].
Back-scattered electron microscope images (BSE) reveal the
textural characteristic of the Si01: polymorphs. Stishovite is Sclar et al. [6] have shown that prismatic to tabular, or
the brightest phase, coesite is grey and quartz black. needle-like, stishovite crystals can form rapidly at high pres-
sures (>7.5 Ga) and at high temperatures (> 900°C). Based
on the occurrence of stishovite observed in this study, we
believe that its fonnation is initiatied during the shock com-
pression stage via the combined effect of conductive heating
from the melted matrix (>900°C) and intra-vein shock rever-
beration (>10 GPa). Additional heat from the melt generated
in the shock vein may have facilitated the continued growth
of stishovite needles after the shock pulse.
References: [J] Matson D.W. Sharma S.K. and Philpotts

l.A. (1986) Raman spectra of some tectosilicatesa and of-
glasses along the orthoclase-anorthite and nepheline-
anorthite joins. American Mineralogist, 71, 694-704.
[2] MartinI J.EJ. (1991) The nature, distribution and gene-
sis of the coesite and stishovite associated with pseudotachy-
lite of the Vredefort Dome, South Africa. Earth and Planeta-
Electron back-scattered diffraction patterns for stishovite. ry Science Letters, J03, 285-300. [3J SlOmer D. and Lan-
genhorst F. (1994) Shock metamorphism of quartz in nature
In addition to the standard spectral measurement, the Raman and experiment: I. Basic observation and theory. Meteoritics
instrument can be coupled to an optical microscope to gener- 29, 155-J81. [4] Hudgins J.A. Walton E.L. Spray J.G.
ate "chemical images" of samples as acquired by Raman (2007) Mineralogy, petrology and shock history of lunar
imaging or Raman mapping techniques controlled by WiRE metrorite Say al Uhaymir 300: a crystalline impact-melt
2.0 software. The intensity of Raman bands at 521 cm- 1 (coe-
breccia. Meteoritics and Planetary Science 42, 1763-1779.
site) and 231 cm· 1 (stishovite) were mapped to investigate
[5] Gillet, P., Ingrin, J., and Chopin, C. (1984). Coesite in
phase distributions to better understand shock wave-
materials interactions and shock heterogeneities. subducted continental crust. Earth and Planetary Science
Letters 70, 426-436. [6] Sclar, C.B., L.C. Carrison, and G.G.
Results and Discussion: It has been indicated from a Cocks. (1964) Stishovite: thermal dependence of crystal
number of previous studies that stishovite and coesite are habit. Science 144,833-835.
formed and metastably preserved in rocks that experience
shock-induced metamorphism [2, 3). At Vredefort. masses of
microcrystalline coesite and stishovite «0.5 to 6 11m) occur
in shocked metasedimentary rocks. The high-pressure phases
Raman Spectra of a Fine-Grained Labradorite Sample Heated to Typical

Mercury Dayside Temperatures. Ute Bottger', lorn Helbert', Alessandro Maturilli " and Heinz-
Wilhelm Hubers', 'Institute of Planetary Research, German Aerospace Center (DLR), Rutherfordstr. 2, 12489 Berlin-
Adlershof, Germany (ute.boettger@dlr.de)
Introduction
Analyzing the surface composition of Mercury's regolith

from remote-sensing measurements is a challenging task.
To support the interpretation of data of recent missions
like MESSENGER (NASA) and to prepare future mis-
sions like BepiColombo (ESA) to Mercury measure-
ments of surface material analogues must be performed
on Earth.
Labradorite is considered as a Mercury surface ana-
logue and is investigated for a better understanding the
processes on the surface of Mercury. For this purpose
§ t==',;=='~~~_--,,~,,- =- =-_~,=~,,- __
~,-
mid-infrared and Raman measurements of labradorite
were performed in the Institute of Planetary Research
at DLR in Berlin. The mid-infrared-measurements were Figure 1: Raman spectrum of labradorite, powder grain
first presented by Helbert and Maturilli [1]. These spec- size <25J-lm.
tra indicate significant changes of the spectral features in
the mid-infrared region at high temperatures and some of
these changes were stili observable after cooling the sam-
ple to room temperature. This led Helbert and Maturilli
(l] to the assumption that labradorite during the heat-
ing process undergoes an irreversible structural change.
Here we present the first measurements of Raman spec~
tra of the same samples of labradorite which are comple-
mentary to the mid-infrared measurements. In the Ra-
man spectra a change is seen as well, which supports the
asswnption of the structural change.
The experimental setup and samples
Two samples of labradorite were investigated. The sam-

ples were powder like with a grain size less than 25 p.m. Figure 2: Raman spectrum of labradorite after heating
The first sample was measured without any prior treat- and subsequent cooling procedure, powder grain size
ment. The second sample was heated for three days at a <25I'm.
temperature of 420°C which corresponds to temperature
on the days ide of Mercury. After heating it was cooled
to room temperature and than analyzed.
The measurements were performed with a Raman Results
microscope alpha300 system from Witec [2]. The excita-
tion source is a Nd:Yag laser of 532 run wavelength and The spectra of both labradorite samples are shown in the
a maximum power of 100 mW. The spectral resolution figures 1 and 2. As can be seen both samples have differ-
of the spectrometer is 3 em-I. The Raman microscope ent spectra. The main feature is the change of ratio of the
has imaging capability. 2500 spectra were taken over an two main peaks of the spectrum around 511 cm- 1 and
area of 0.5 p.m diameter. The measurement time for one 283 em-I. This change in the ratio will be analyzed. We
spectrum was 1 second. The spectra were averaged and suppose that structural changes induced by the heating
used for analysis. and cooling caused the change.
References
[I] J. Helbert and A. Maturilli. The emissivity ofa fine·grained
labradorite sample at typical Mercury dayside tempera-
tures, submitted. EPSL,2009.
(2] WITee focus innovations. a1pha300, 2008. URL
http://www.witec.de/en/products/raman/
alpha300r/ .
CHARACfERIZATJON BY CATHODOLUMINESCENCE SPECTROSCOPY OF SILICA PHASES AS

INDICATOR OF THE SHOCK IN METEORITES. H. Chennaoui Aoudjehane"', A. Jambon', O. Boudouma',
B. Reynard 4, 'Hassan II University Aln Chock, Faculty of Sciences, Geology Department, BP 5366 Maarif Casa-
blanca Morocco (e-mail: chennaouih@yahoo.fr). 2Universite Pierre et Marie Curie-Paris6 Laboratoire MAGIE,
Case 110,4 place Jussieu, 75252 Paris, France (e-mail: jambon@upmc.fr). 3Universite Pierre et Marie Curie-Paris6
Service de microscopie electronique it. balayage, Case 110, 4 place Jussieu 75252 Paris, France (e-mail:
boudouma@ccr.jussieu.fr), 4Laboratoire des Sciences de la Terre, CNRS UMR 5570, ENS Lyon, 46 Allee d'ltalie,
69364 Lyon Cedex 7, France,CNRS UMR 6112 (e-mail: breynard@ens-Iyon.fr).
Introduction: The intensity of the shock in mete- quartz may result from crystallization at depth rather
orites have been discussed by many authors and is still than transformation by shock. In enstatite chondrites,
a subject of controversy [1-5]. We work on using the however the occurrence of quartz is less likely to result
mineralogical state of silica in meteorites in order to from a confining pressure; the intensity of the shock in
constrain the shock conditions and intensity. Identifi- these type of meteorites is about 1 GPa.
cation of amorphous or crystallized silica phases: Discussion: CL is an interesting technique: it al-
quartz, tridymite, cristobalite, stishovite, seifertite, lows to identify seifertite unambiguously, whereas
high pressure silica glass is performed by cathodolu- other spectroscopic method are inefficient. This tech-
minescence (CL) spectroscopy on the SEM of the nique is rapid, efficient, it does not require any specific
University Pierre and Marie Curie Paris 6 France Pan- preparation of polished sections. Application to feld-
chromatic images and spectra for each silica phase spars is in progress. A number of additional minerals
have been recorded. All spectra have been collected, may be potentialtargets.
Raman spectroscopy have been used to calibrated the In agreement with previous studies, martian mete-
technique, that allowed to assign a specific spectrum to orites appear to be the most heavily shocked. The di-
each silica phase. versity of their high pressure phases in one single sec-
tion, underscores the difficulty in estimating the peak
Studied samples: The samples studied are silica shock intensity.
bearing meteorites and some terrestrial rocks (granite
and rhyolite). Studied meteorites are: References: [I] Sharp T.G. et al (1999) Science
Shergottites: NWA 480, NWA 856, NWA 284, 151 1-1513. [2] EI Goresy A. et al. (2000) Science
1069, Los Angeles, Shergolty, Zagarni, 288,632-634. [3] Malavergne V. et al. (2001) MAPS
Nakhlite MIL 03346 [6-8] 36, 1297-1305. [4] El Goresy A. et al. (2004) Jour.
Eucrites : Camel Donga, Juvinas, Phys. Chern. Sol. 65, 1597-1608. [5] Beck P. et aI.
Enstatite Chondrites: Galim (impact melt), (2005) LPSC. XXXVI, #1333. [6) Chennaoui Aoudje-
Saint-Sauveur (EHS), SAH 97158 (EH3) hane H. et al. (2005) MAPS 40, 967-979. [7] Chen-
Experimental techniques: Samples are thin or naoui Aoudjehane H. et al. (2006) LPSC XXXVll Abs-
thick sections. After collecting BSE images covering tract #1036 [8] Chennaoui Aoudjehane H. et al. (2006)
the whole section to find silica areas, images and spec- LPSC XXXVlJ Abstract #1037.
tra of the areas of interest are recorded. CL equipment
was described previously [6]. Images are panchro-
matic, spectra are collected between 200 and 900 nm,
corrected of the transfer function of the system and
transfonned to wavenumbers (cm,I). Several spectra
are collected for each phase. All areas analyzed by CL
were subsequently analyzed by Raman spectroscopy.
Concordance between CL spectra and Raman spectra
allowed us to calibrate the technique.
Results: In shergottites, silica phases are:
stishovite, seifertite [7] and high pressure silica glass.
These phases are frequently connected to melt pockets.
This suggests that the intensity of the shock in shergot-
tites is at least 40 GPa [6]. In the nakhlite MIL 03346
[8), the presence of cristobalite indicates a peak shock
intensity of less than IGPa. In eucrites, we found
mostly cristobalite and tridymite; the occurrence of
18 LPIContributionNo.1473
SPECTRALLY-RESOLVED THERMOLUMINESCENCE ON HYDROTHERMAL ARAGONITE. E. Cres-

po-Feo l , J. Garcia-Guinea], V. Correcher2 and A. Garralon 2 , IMuseo Nacional de Ciencias Naturales- CSIC. C/ Jose
Gutierrez Abascal 2 Madrid 28006 Spain, correspondence author: ecrespo@mncn.csic.es, 2C1EMAT. Av. Complu-
tense 22. Madrid 28040 Spain.
Introduction: The blue thennoluminescence (TL) nm, Hence the TL recording is limited up to just the
behavior and possible associated defects of a natural blue spectra region. The full width at half-maximum
hydrothermal aragonite (CaCO,) from Urals (Russia) (FWHM) value for the filter is 80±16 nm and the peak
has been investigated. Luminescence studies on car- transmittance is 60%. The system is also provided with
bonates have been mainly focused on calcite due to its a source with a dose rate calibrated against a photon
high luminescence response. Conversely, aragonite has source, in a secondary standards laboratory. All the TL
been considered a poor TL material but its abundance measurements were perfonned using a linear heating
in some speleothems, corals and in seafood shells rate of 5°C/s from RT up to 400°C, in a N 2 atmosphere.
makes it interesting for datation or irradiation identifi- Samples were irradiated at RT with a calibrated
cation uses. Studies related to dating shell fossils as 9OSrt'Y beta source with a dose rate of 0.1470 Gy/s.
well as growth periods of corals [1] and mollusk shells Four aliquots of aragonite sample were used for each
[2] are quite common, even though it has been pointed measurement. The incandescent background was di-
out that some biogenic aragonites do not exhibit ther- rectly subtracted from the TL data.
moluminescence [3]. Results and Discussion: Chemical analyses by
Several works have focused on explained how the ICP-OES indicate the presence of impurities as fol-
content of impurities and lattice defects as well as their lows: Si (282.33 ppm), Ba (146.06 ppm), Sr (127.50
distribution in the lattice affect the luminescence re- ppm), Fe (21.85 ppm), Y (5.08 ppm), Mn (4.03 ppm),
sponse [4]. This knowledge is essential for a reliable Nd (3.10 ppm), Ce (2.28 ppm), La (2.26 ppm), Gd
datation data through TL technique. (1.48 ppm), Pr (1.47 ppm), Er (1.33 ppm), and Yb
Samples and Experimental Procedure: The (0.75 ppm). It is important to note that most of these
studied specimen is a fibrous-radiated aragonite with elements are luminescence activators and only Fe be-
very thin white opaque fibers from Urals (Russia). haves as a quencher in the aragonite lattice.
Inductively Coupled Plasma-Optical Emission Spec-
troscopy (ICP-OES) analysis was performed to deter-
minate the amount of impurities present in the mineral.
The sample was analyzed in a Spectro ICP-CCD spec-
trometer with 1400 mW, 14 L/min of refrigeration gas
flux, 0.85 L1min auxiliary gas, 0.95 L1min nebulizator
gas, 0.25 L1min additional gas, and 1.0 mL/min sample
aspiration velocity. All elements detection limits are
between 1 and 5 ppb, and the sample was measured a
total of 9 times.
MicroRaman spectra were perfonned for checking
the homogeneity of the mineral by a Thenno-Scientific
DRX Raman. The analytical conditions were 532 nm
laser with a 100% power of lOmW, exposition time to
laser of 1 s, and one acquisition. 3430 3440 3450 3460 3410 3480 3490 3500 3510
The 3D-TL spectrum was taken on a high-sensivity Position (micrometers)
wavelength multiplexed system with f/2.2 optics de- Fig.I. Hyperspectral image Raman ofaragonite fi~
veloped at Sussex, with detection between 200 and bers.
800 nrn and a spectral resolution of -4 nm at a heating
rate of 2.Soe/min. TL measurements were done after a A hyperspectral Raman plot of aragonite fibers is
dose rate of 50Gy using a Philips X-ray tube. illustrate in Fig 1. The colourscale directly corresponds
Natural and irradiated glow curves were obtained with the intensity of the Raman peak at 1084 em-I. The
using an automated Ris0 TL system model DA-12. variation in Raman intensity at different points can be
This reader is provided with an EM! 9635 QA pho- attributed to the roughness of the surface if the points
tomultiplier and the emissions were observed through are not in the same focal plane but the analyses were
a blue filter (a FIB002 of the MeUes-Griot Company) perfonned on a polishing substrate for avoiding this
in where the transmission wavelength is peaked at 320 phenomenon. There is no observable difference be-
Conference on Micro~Raman Spectroscopy and Luminescence Studies 19
tween single spectra of both fibers but intensity dis- assume this explanation as cause for the 320 nm emis-
parities can probably be attributed to slight variations sion of aragonite.
in impurities content. It has been reported that during Fig 3 displays three TL glow curves of a natural
aragonite growing substituting cations (e.g. Sr, Ba, aliquot, a pre-irradiated natural aliquot with 24Gy, and
Mg, and Mn) enter in different concentration creating the curve corresponding with spectra region 1 in Fig
heterogeneous distribution [8]. 2b. The natural curve arises from 180° to 325°C exhib-
@ iting a maxima peak at -246°C. However, the beta-
irradiated aliquot samples show a more complex curve
where two main peaks are composed by in two addi-
tional signals. The four maxima peaks are as follows:
-120°C; -160°C; -242°C; and -294°C. The UV-blue
emission appears at the same temperature for both ir-
radiated aliquots pointing to a possible structural ori-
gin of it. The observed glow peak in both, natural and
24 Gy irradiated TL curves, does not appear in the
@ spectra after 50 Gy irradiation. It seems that the ap-
plied radiation dose has been enough for eliminate the
natural thermoluminescence.
120 - ---- Natural TL
e 300
70
-..-.._. TL after 24 Gj X-Ray
- TL after 50 Gj X-Ray
•
00
.3
~ 200
, SO
.
E
100
""f 40
2Oko=::::;3JOO;::::i::;40!oO;=':::::5~oko::J::::;6~0~O :::":'::"'*-oo;=':::::elaoo
'"
.s SO
20
Wavelength (nm)
\0
Fig.2. JD-TL emission spectra (a) and contour plot
\~~/¥~~.
(b) for the fibrous arogonite. See text for glow peaks 0
100 200 300 400 500
numbers descriptions. Temperature (0C)
Fig.3. Natural and after 24 Gy X-Ray irradiation
Fig 2a and 2b show the 3D-TL and TL contour plot glow curves using a filter peaked at 320nm. UV-blue
for the Urals aragonite, in where the following glow
signal (320 nm) numbered 1 from Fig 2b is also dis-
peaks can be observed: I) -120°C, -320 nm; 2) played.
-120°C, -485 nm; 3) -120°C, -575 nm; and 4) - The blue spectra region of the TL emissions of
125°C, -640 nm. These spectral emission bands are in
CaC0 3 materials is commonly used for dating pur-
accordance with previous works that have interpreted poses. Hence, here we propose further experimental
them as 4Eg, 4p(4T Jg), ~2g, 4G(+rlg)~6S Mn 2+ ion transi-
work on this item.
tions [4]. Taking into consideration the amount ofREE References: [1] Isdale P. (1984) Nature. 310, 578-
present in the sample, it seems strange the absent of
579. [2] Ninagawa et al. (1992) Quat. Sci. Rev.. 11,
luminescence related to them though no works have
121-126. [3] Johnson N.M. (1960) J Sediment. Pe-
reported this possibility. Moreover, it is commonly
trol., 30, 305-313. [4] Calderon et al (1996) Radiat.
assumed that higher wavenumbers signals are related
Meas., 26, 719-731. [5] Gotte T. and Richter D.K.
to point defects due to impurities whereas UV-blue (2009) Sedimentology, 56, 483-492. [6] Finch A.A.
emissions correspond to structural defects [9]. The and Allison N. (2007) Min. Mag., 71, 539-552. [7]
presence of Si in carbonates has been explained as a
Garcia-Guinea J. et al. (2007) Nucl. Instrum. Met.h. A,
selective adsorption of silicate anions, such us
580, 648-651. [8] Terada T. et al. (2003) J Cryst.
SiO(OH), and Si 4 0,(OH)" along determined growth Growth, 253, 435-444 . [9] Garcia-Guinea 1. et al.
directions [10]. The possible presence of water and (2009) Rad. Meas., accepted.
hydrous silicates between carbonate fibers generate Acknowledgements: This work was partly sup-
reactive bonded hydroxyl groups and non-bridging ported by JAE-Doc CSIC contract and MATERNAS
oxygen that produce the UV-blue emission [11]. We (CAM) S05051MATI0094 project.
LuCIDD: A LUMINESCENCE INSTRUMENT WITH CONFOCAL AND IMAGING UNITS FOR

DATING AND DOSIMETRY. R. DeWitt' and D.M. Klein' 'Department of Physics, Oklahoma State University,
145 PS II, Stillwater, OK 74078, USA, rkalchg@okstate.edu.
Introduction: We describe the development of a The potassium in other feldspars on the other band
Luminescence instrument with .confocal and Imaging causes a high dose rate inside the grains. A statistical
units for .Qating and .Qosimetry (LuCIDD) enabling approach for detennination of dose and dose rate can
spatially resolved optically stimulated luminescence only yield estimates of uncertain accuracy.
(OSL) measurements. Requirements of an instrument for surface dat-
OSL dating is a well-established technique for age- ing: (I) The measurement of macroscopic bulk sam-
dating the last sunlight exposure of sediments, i.e. time ples, without the need to separate the sample into sin-
of deposition, ranging from recent decades to about gle grains. This prevents an ablation of the surface and
5
10 years ago. The technique measures the lumines- a splitting of grains. (2) The penetration depth of the
cence emitted from the sample during stimulation with stimulation light must be controlled to make possible
light in the laboratory. The OSL intensity is propor- the control of the depth from which the detected lumi-
tional to the absorbed radiation dose, which is then nescence originates. In this way only the OSL signal
divided by the dose rate to yield the age of the deposit. from those depths is measured for which full solar
The fundamental premise of OSL dating is that the resetting during sunlight exposure is expected. (3) The
sediments to be dated were exposed to sufficient measurement of spatially resolved OSL to detennine
amounts of light at the time of deposition to erase the spatial variations in the radiation field.
previously accumulated signal. Luminescence imaging: Several attempts have
Limitations of current OSL dating techniques: been made to image the luminescence emission from
Commercially available instruments, such as the samples in order to individually monitor the lumines-
widely used Ris. TLI OSL readers [1,2], are designed cence from each single grain, e.g. image intensifiers
for measurements with grains not bigger than 1-2 mm. [4], highly sensitive photographic films [5,6], or CCD
The grains have to be removed from their surrounding chips (7,8,9]. Bailiff and Mikhailik [10] developed a
material for analysis. The total dose for a sample vol- scanning system with a 250 11m laser spot to stimulate
ume is calculated statistically and compared to an av· a selected area of a brick sample. These experimental
erage dose rate for the bulk volume. Three limitations systems allow limited spatial measurements with bulk
make those instruments unsuitable for bulk materials samples. Depth control, however, was not possible in
like rock-surfaces. all cases.
Solar resetting: Only the very surface of the rock Confocal system: Confocal microscopy systems
has its OSL zeroed during sunlight exposure. With offer the spatial resolution of microscopes and addi-
increasing depth the light intensity is reduced and the tionally allow control of the depth of field. They are
OSL is not reset (3). Any "residual" OSL signal will widely used for fluorescence experiments, and there-
lead to inaccurate age detennination. In principle it is fore lend themselves naturally to OSL measurements.
possible to separate tbe previously fully bleached sur- The working principle is detailed in Figure 1.
face material of an embedded or overturned rock, but A lens is focusing a laser beam to fully illuminate
uncertainties over the correct cutting depth will lead to the "stimulation aperture", located in the focal plane of
corresponding age uncertainties. a subsequent second lens. The laser beam is then re-
Sample preparation: Most rocks consist of several flected by a beam splitter and passes through the mi-
different minerals and grain sizes. To obtain individual croscope objective, to form an intense diffraction-
mineral grains the rock must be crushed. Beta radia- limited spot on the sample surface. The emitted lumi-
tion, with a range of2-3 mm, does not unifonnly pene- nescence passes back through the objective and the
trate mineral grains and is attenuated. Alpha radiation beam splitter. A lens focuses the luminescence beam
only has a range of about 10 ~m. To correct for these on the "detection aperture", which is again located in
variable and anisotropic dose rates, defined grain sizes the focal plane of the lens. Luminescence that is emit-
must be used for the measurements. The crushing and ted above and below the objective focal plane is not
breaking of grains destroys this information. confocal with the detection pinhole and is therefore not
Dose rate: Rock surfaces are interfaces with com· delivered through the pinhole aperture. With this setup
positional and radiation dose-rate variations and gradi. the penetration depth of the stimulation light can be
eots. Rock and surrounding material both contribute to controlled. The measured signal will only come from
the total dose rate. Quartz and plagioclase minerals are mineral grains at the surface, which have been suffi-
mostly assumed not to contain radioactive nuclides. ciently reset during the last sunlight exposure. Reduc-
tion of scattered light leads to an improved signal-to-

noise ratio. Confocal microscopy systems offer high
spatial resolution and allow field depth control. The
working principle is therefore an ideal basis for a new
OSL instrument.
Inflrity COll'ectad
............ len.se System and
..-- Defection
Aper1ule
subsurface.
surface. ----+ _ _1-__ out of
In focot plane - - _. - - -. - _....... .......- focal plana
Figure 1: Working principle of the confocal unit.
LuCIDD, a different approach to OSL dating

instrumentation: LuCIDD will be based on a confo-
cal microscope and will allow measurements of bulk
samples with spatial resolution and control of light
penetration. The instrument will will consist of (I) an
optical setup including lasers for stimulation of the
samples, (2) a confocal arrangement for laser scanning
and detection of luminescence from a controlled sam-
ple volume at a high spatial resolution, (3) an imaging
unit with CCD camera, (4) facilities for irradiation,
bleaching and temperature control. The instrument will
be controlled with a PC and allow fully-automated
measurements over a wide temperature and wave-
length range.
Acknowledgements: This work is supported by
the NSF - Major Research Instrumentation Program,
Grant # 0722552
References: [I] BBtter Jensen L. et al. (2000) Ra-
dial. Meas., 32, 523-528. [2] BBtter-Jensen L. et al.
(2003). Radial. Meas., 37, 535-541. [3] Habermann J.
et al. (2000) Radial. Meas., 32, 847-851. [4] Huntley
DJ. and Kirkey U. (1985) Ancienl n, 3, 1-4.
[5) Hashimoto T. et al. (1986) Radial. Meas., JI, 229-
235. [6) Hashimoto T. et a1. (1995) Radial. Meas., 24,
227-237. [7) Duller GAT. et al. (1997). Radial.
Meas., 27, 91-99. [8) Baril M.R. (2002) PhD thesis,
Simon Fraser University, Burnaby (B.C.), Kanada.
[9] Greilich S. and Wagner G.A. (2006) Radial. Meas.,
41, 738-743. [10] Bailiff I.K. and Mikhailik V.B.
(2003) Radial. Meas, 37,151-159.
22 LPI Contribution No. /473
DATING THE LIGHT SHIELDED SURFACE OF COBBLES TO RECONSTRUCT PAST SEA LEVELS
IN ANTARCTICA. R. DeWitt', P. Kouremenos', A. M. Drewry' and A. R. Simms', 'Department of Physics,
Oklahoma State University, 145 PS II, Stillwater, OK 74078, USA, rkalchg@okstate.edu, , Boone Pickens School
of Geology, Oklahoma State University, Stillwater, OK 74078, USA.
Introduction: We carried out a preliminary study sunlight was when they were turned over in the swash
using the optically stimulated luminescence (OSL) zone at sea level (Figure I). As the land rose, these
signal from cobbles with the goal of dating raised deposits became isolated from the marine processes
beaches in Antarctica. that created them. Dating the last sunlight exposure of
Melting of the Antarctic Ice Sheet contributes to the cobble-underside, can therfore be used to create
sea-level rises, but also leads to an uplift: of the conti- sea-level curves. We describe the rationale and test the
nent due to the weight reduction. Paleo-shorelines can reliability of a novel approach to reconstructing past
therefore be used to establish the thickness of the ice sea levels in Antarctica.
sheet through time and to create relative sea-level Field work: For this preliminary project we col-
curves for Antarctica [I]. Sea-level curves for Antarc- lected 3 cobbles from each raised marine feature.
tica have been derived from raised beaches [2] using Samples were collected from 3 sites around Maxwell
radiocarbon dating, which is limited by the availability Bay in the South Shetland Islands. In order to shield
of organic material, its relatively short age range not the cobbles from light during sampling, we used a
encompassing the last interglacial period, the possibil- thick black tarp made from heavy duty darkroom cloth.
ity that the samples were reworked, and the ambiguity The room underneath was large enough to provide
of the radiocarbon reservoir [3]. working space for two people. Cobbles frozen in the
Here we report on a novel use of OSL to recon- ground were removed with a spade or a pickaxe and
struct past sea levels from raised beaches and boulder wrapped in black plastic. Light was provided by flash-
pavements in the South Shetland Islands of the Antarc- lights with red filters. For each OSL-sample we fur-
tic Peninsula. The OSL technique detennines the time thermore collected representative surrounding rocks
elapsed since the last exposure to sunlight, i.e. the time and the underlying material for low-level Ge gamma
of deposition. OSL does not have the same limitations spectroscopy in the laboratory.
as radiocarbon dating because quartz is generally plen- Experimental Approach: We isolated mineral
tiful on the Earth's surface, OSL is free of reservoir grains from the outer I mm of the underside of the
effects, and reworking destroys the OSL signal. In cobbles with a diamond saw in a dark room. The blade
addition, OSL has a longer age range up to 500,000 was water cooled to prevent local heating of the sam-
years with an age-uncertainty of 10% [4]. ples. The slices were carefully crushed with pestle and
mortar as is conventionally done in pottery dating and
quartz separates were prepared. We used a SAR pro-
cedure with high-temperature OSL bleaching [6] to
measure the equivalent dose. The number of aliquots
depended on the amount of quartz extracted from the
samples, but was normally not less than 12. The dose
....... rate was deteffilined with low-level gamma spectrome-
try of the surrounding material and the crushed rocks
themselves. All quartz samples have been found to be
Figure t: Diagram illustrating boulder beaches contaminated with feldspar and fading corrections
around the Antarctic Peninsula. Note that under- were applied as suggested by Auclaire et a1. [7].
sides of cobbles in Band C have not been exposed Bleaching: To investigate the suitability of the
to sunlight since they were in the swash zone A. measurement procedure we first tested the resetting of
the signal by sunlight. We irradiated slices of a granite
cobble with a 6OCO source and exposed the Slacked
Traditionally, OSL is conducted on sand grains
slices to sunlight for 1 hour. The slices were crushed
from dunes, rivers, or beach ridges. Most of the sedi-
and quartz separates were prepared. The measured
ment in beaches along Antarctic shorelines comes
signals from 12 aliquots per slice were normalized to a
from frost cracking of local cliffs or from till [5], re-
test dose and the average is plotted in Figure 2.
sulting in mostly coarse-grained material such as cob-
Sunlight penetrates up to 5 mm into the rock. After
bles and boulders. The last time the cobbles from
one hour 13% of the total signal is left. To ensure that
raised beaches and boulder pavements were exposed to
the rocks are completely bleached in a natural setting

we investigated the upper surface of two rocks col-
.LlL
12
lected from raised beaches in Antarctica. 4 aliquots of -
each rock were measured and none showed a statisti-
10
T ._- - ~=-=tJL
-f J.1J~~ .
cally significant OSL signal above background.
I.S j jj
±- •'~ -
1.'
1.3 -;-'"
12
~{-i j
..• "
~ 0.9
1.0
.;•
- -
• OSL, OUf Elevations
"• OSLo Geospatial Elevations
..•
2
0.'
."
0.7
"c
1
~
o.s o
0 0.'
o 500 1000 1500 2000
z Calendar Age (yrs)
0.'
0.3
0.2
0.1 Figure 3: A comparison between our OSL ages and
0.0 other sea-level indicators from across the South
0 2 4 6 8 10 12 14 16 18
Depth in rock (mm)
Shetland Islands. Gray circles represent the age-
elevation relationship from samples taken from
Byers Peninsula and Maxwell Bay
Figure 2: Bleaching experiment with a sliced gran-
ite sample. Sunlight penetrates Smm deep into the Acknowledgements: This work was supported by the
rock. NSF - Office of Polar Programs, SGER 0724929.
Results: We obtained ages for 8 samples from 3 References: [I] Nakada, M. and Lambeck, K. (1987)
sites around Maxwell Bay in the South Shetland Is- Geophys J Roy Astr S, 90, 171-224. [2] Hall, B.L. et
lands. The OSL ages are internally consistent with a al. (2004). Global Planet Change, 42, 241-263.
"zero" age for the modem beach, multiple ages from [3] Berkman P. A. et al. (1996) Geophys Res Lett, 23,
the same beach ridge agreeing within error limits, and
363. [4] Booer-Jensen L. et a1. (2003) Optically Stimu-
lated Luminescence Dosimetry (Elsevier, Amsterdam,
higher beaches dating older than lower beaches from
2003), pp. 355. [5] Hansom, J.D. and Kirk, R.M.
the same locale. In addition, our OSL ages agree with
(1989) Essener Geographische Arbeiten, 18, 211-236_
sea-level curves based on radiocarbon dating (Fig-
[6] Wintle A.G and Murray A.S. (2006) Radiat Meas,
ure 3). Our new approach to dating raised beaches in
37,487. [7] M. Auclair et al. (2003) Radiat Meas, 41,
Antarctica appears robust. As the material needed to
369.
obtain OSL ages is prevalent, our method will allow
for the creation of sea-level curves in many areas pre-
viously thought impossible within Antarctica and other
polar coastlines.
ODIN: A PROTOTYPE MI IATURE LUMINESCENCE INSTRUMENT FOR DATING OF MARTIAN

REGOLITH. R. DeWitt', S. W. S. McKeever', M. W. Blair' and D. K. Reust', 'Department of Physics, Okla-
homa State University, 145 PS IT, Stillwater, OK 74078, USA, rkalchg@okstate.edu, 'Los Alamos National Labo-
ratory, Earth and Environmental Sciences Division, MS J495, Los Alamos, NM 87545, USA. 'ICx Nomadics Inc.,
1024 S. Innovation Way, Stillwater, OK 74074, USA.
Introduction: We describe a prototype design for near-surface deposits on Mars. The primary radiation
a robotic luminescence reader and discuss the con- field on Mars is from galactic cosmic rays (OCR) and
straints on the design of a space-approved instrument solar energetic particles (SEP). This is significant as
and the handling of the sample material. the efficiency of signal production varies with the type
The Martian surface exhibits abundant evidence of of radiation. Specifically, low-energy high-Z particles
having undergone a complex geologic and climatic have a high ionization power, or large Linear Energy
evolution. Aeolian, fluvial, periglacial, and volcanic Transfer (LET). Such particles are not as efficient in
processes appear to have remained active through the producing OSL signals since the high ionization den-
present day and evidence even points to active global sity in the track of the particle as it traverses through
climate change. Establishing an accurate chronology is the material leads to saturation of the signal. The com-
critical to addressing many of the outstanding ques- position of the radiation and, therefore, LET change
tions regarding the climate of the planet. The goal of with depth due to scattering and absorption of the par-
our Optical Dating Instrument (ODIN) is to provide ticles. Cosmic ray spectra are dominated by the lower
this chronological context for processes that have oc- LET parts of the spectrum. For low LET irradiations,
curred during the last <IMa. the luminescence efficiency is -1, with respect to 6OCO
Optically Stimulated Luminescence (OSL) Dating or 90Sr radiation. As a result, one can use a single low-
Applied to Martian Surface Materials: OSL dating LET radiation source (e.g., x-rays) to calibrate the ma-
works on the premise that the luminescence signal, terials, with only a small error introduced (5-10%;
emitted by certain minerals during controlled light based on the under-lover-response of AhO) for proton
exposure is directly proportional to the absorbed radia- radiation with respect to gamma, plus a small error for
tion dose. If the dose rate due to radioactive nuclides ignoring the efficiency of the high LET component).
and cosmic radiation is known, the burial age can be Thus, from a calibration of the signal response versus
calculated by dividing dose by dose rate. OSL is an dose, one can determine the equivalent dose corre-
established dating technique for terrestrial fluvial and sponding to the measured natural signal on Mars.
aeolian deposits, and age determinations within 5% Natural dose rate: The dose rate will not be con-
are routinely possible. Any OSL method for Martian stant over the lifetime of buried minerals, representing
regolith must be robust and suitable for the challenges a time-varying dose rate. One can imagine three basic
that may be encountered on Mars. scenarios for the natural radiation environment of bur-
Measurement procedure and temperature depend- ied sediment. (1) The primary contribution to the dose
ence: An in situ OSL dating instrument for Martian with shallow stable burial comes from GCR and SEPs,
regolith samples will likely not allow chemical treat- with negligible contributions from U, Th and K up to
ment and mineral separation. Kalchgruber et al. [1] regolith depths of a few meters. (2) Rapid, deep burial
used mineral mixtures to approximate the type of po· (e.g., a massive flood event) would be minimally af-
lymineralic samples that may be found on the Martian fected by external OCR and SEP, with primary contri-
surface. Using a combined infrared and blue stimula- butions from background U, Th and K radiation. (3)
tion method they were able to measure a known For shallow initial burial with deeper burial over time,
1600 Oy laboratory dose with 6. J % accuracy using one would need to model the burial rate and calculate
the IR stimulated signal and 4.0% for the blue stimu- the time-dependence of the subsequent dose rate.
lated signal. Low-temperature measurements and Anticipated age limits and uncertainties: Assum-
simulations indicate that known doses delivered at low ing a lower measurahle dose limit of 5 Oy [I] and an
temperatures can be effectively estimated if the stimu- average surface dose rate of 100 mOy/year [5], the
lation temperature is considerably greater than the lower age limit for OSL dating can be expected to be a
highest temperature during irradiation-Le., in the case few decades. With an upper measurahle dose limit of
of Mars at least 80-100°C [2]. Thus an OSL instrument 15000y, the upper age limit would be only 10,000
must provide IR. and blue stimulation and a heating years and, thus, considerably lower than on Earth. It
option beyond 100°C. has to be taken into account, however, that the dose
Radiation environment and calibration source: rate decreases rapidly with increasing burial depth
Radioactive nuclides play only a minor role in the since is is dominated by OCR and SEP. At 3-4 m
depth and a background dose-rate of 0.5 mGylyear controlled from a notebook computer. Testing of the
[6,7] the upper age limit would be 3 Ma. Depending on system with a martian regolith simulant and dose re~
the burial rate, the upper age limit is, therefore, ex- covery experiments resulted in 2.5% reproducibility.
pected to be in the region of several lOs years. Dose
rate variations with depth depend on the model used,
but are in the range of 50% for 2 m burial depth [7,8].
For an initial approximation the age can be bracketed
by calculating a minimum age based on the surface
dose rate, and a maximum age based on the dose rate
at the depth from which the sample is recovered. An
improved age value can then be detennined using bur-
ial models. A better accuracy can be achieved, if sev-
eral samples are obtained from a depth profile. Then,
burial models for lower samples can be based on the
ages obtained for the upper samples.
aDI T: The basic requirements for all components
of spacecraft in~truments are low power, low weight,
low volume and economical data acquisition. A rule of
thumb for a robotic luminescence instrument would be
2-3 kg mass, housed in a package of shoebox-size, and
with several watts electrical power consumption. The
instrument described here is a prototype and not meant
for a space mission itself. It is nevertheless the goal to
design a system with these requirements in view.
An optical dating instrument requires light Figure 1: ODlN prototype. The diameter of the
sources for sample stimulation, a photo detector for turntable is 3.75".
sensing the luminescence signal, a heater to empty
unstable traps and control the stimulation temperature, Acknowledgements: The project was funded by
and a radiation source to calibrate samples. The proto- NASA (JPL Contract No. 1265427 under grant NASA
type of ODIN is shown in Figure I. Aliquots are de- RTOP No. 344-36-55-19) and a Research Initiation
posited into copper cups and transported from the Grant from Oklahoma NASA EPSCoR.
loading position to the measurement position via a
stepper-motar-driven turntable. The OSL unit per- References: [I] Kalchgruber R. et al. (2006) Radial.
fonns optical stimulation and irradiation at the position Meas., 41, 762-767. [2] Blair M.W. et al. (2006) Rad
under the PMT. Subsamples can be stimulated with Prot. Dosim., 119,454-457. [3] Aitken M.J. (1998) An
blue (470 nm, 50 mWlcm' on the aliquot) or IR LEOs Introduction to Optical Dating. Academic Press, p. 44.
(870 nm, 8.5 mWIcm' on the aliquot). Broadband in- [4] Deo S. et al. LPS XXXVI 36, Abstract #1029. [5]
terference filters are used to narrow the bandwidth of Saganti P.B. et al (2004) Space Sci. Rev., 110, 143-
the stimulation light and to prevent an overlap with the 156. [6] Pavlov AX. et al. (2002) Planet. Space Sci.,
detection band. A Hamamatsu H93l9-ll photomulti- 50, 669-673. [7] McKeever S.W.S. et al. (2003) Ra-
plier with filters is used to detect the luminescence dial. Meas., 37, 527-534. [8] Morthekai P. et al.
signal in the band 330 to 370 nm. A spring-loaded (2007) Nucl. Inst. Meth. Phys. Re.s A, 580, 667-670.
heater at the position under the PMT allows the tem-
perature to be ramped at computer-controlled rates.
The upper temperature limit is 200 o e, a stimulation
temperature expected to be sufficient for Martian con-
ditions [2]. A MOXTEK Bullet miniature x-ray source
(4W, 35 kY,) is used for dose calibration. A copper
cover blocks light and x-rays from queued samples in
the aliquot disk. One subsample at a time is presented
for irradiation or stimulation. The expected peak
power of the system in operation is 5-6 W. A software
program was developed to control the required se-
quence of heating, cooling, optical stimulation, OSL
measurement and irradiation. The OSL system can be
26 LP/ Contribution No. /473
Confocal Raman Imaging in Geosciences
Thomas Dieing, Andrea Jauss, Ute Schmidt, and Jan Toporski
W1Tec GmbH, Hoerveisingerweg 6, 89081 Uim Germany
Description of geological materials may require detailed knowledge of their compositional

properties on the nanometer scale, leading to a growing demand for analytical methods that
provide information in addition to techniques routinely applied in geosciences. Confocal
Raman microscopy provides insights regarding chemical variation and distribution, structural
information, or material stress at high spatial resolution without inflicting damage or using
invasive techniques such as staining. This technique is a tool that provides information
complimentary to data obtained by electron microprobe (EMP), energy dispersive X-ray
analysis (EDX), or secondary ion mass spectrometry (SIMS). In addition to the quantitative
and semi- quantitative elemental and/or isotopic data acquired by these techniques, confocal
Raman microscopy contributes to the visualization of spatial molecular information over a
defined sample area. Furthermore, considering that most geo-materials are transparent from
the NUV to the VIS and NIR to some degree, this information can be obtained three-
dimensionally due to the confocal set-up of the microscopes.
The power of Raman imaging stems from the highly detailed chemical information revealed
by molecular vibrational spectra. Due to Raman spectroscopy being an inelastic light
scattering process, acquisition of Raman spectra may be the time-limiting factor in Raman
imaging. By combining an ultrahigh throughput confocal microscope with an extremely
sensitive spectroscopy system, the integration time for the acquisition of Raman spectra can
be reduced to few milliseconds. This short integration time enables the acquisition of arrays of
thousands of complete Raman spectra within minutes. In addition, the confocal setup reduces
unwanted background signals, enhances contrast and provides depth information for
translucent materials. The images are evaluated from the two dimensional array of the
collected Raman spectra by isolating spectral characteristics such as peak intensity, width,
position, etc. Differences in chemical composition can be analyzed with a resolution down to
-200 urn.
This contribution aims to outline the key features required for confocal Raman microscopy
and demonstrate the capabilities with examples from a variety of geological samples.
Conference on Micro-Raman Speclroscopy and Luminescence Sludies 27
IMPULSE CATHODOLUMINESCENCE SILICATE GLASSES. V.E. Eremyashev'~

IInstitute of Mineralogy UB RAS. 2South Ural State University
The method impulse cathodoluminescence (JCL) was

tested as a new method of investigation of structural
feathers synthetic alkaline silicate glasses. Some sam-
ples of silicate glasses Na,O-AJ,O,-SiO, join with
different Na and Al content was synthesized for this
study. They were prepared using chemically pure
Si02 , Ah03 and Na2C0 3 melted at 1200 °C in air
atmosphere for 24 h and quenched in air.
The spectral analysis of cathodoluminescence was
executed by CLAV1-R impulse spectrometer (lEP of
UB of RAS). The major power and impulse mode has
ensured an opportunity to receive spectra for these
samples. One dominant band different shape observed
in ICL spectra of all silicate glasses. With increase
alkaline in composition of glass intensities of this
band increase. Width of band is more in silicate
glasses spectra with aluminum due to the high-
wavelength shoulder.
Implications of the spectral data for the glass structure
are discussed. Structure of these glasses is different
and part of non-bridge oxygen's atoms is increase
with increase alkaline in glasses [1-4].
It was shown, that intensities of dominant band in CL
spectra depend on part of non-bridge oxygen's atoms,
bonding with alkaline and earth alkaline atoms.
Shoulder of band are observed in AI-rich glasses and
increase with increase of AI content. Another Na posi~
tion is a parent of this changes in spectra.
This result correlated with NMR, RAMA and IR
data for these glasses, so ICL method can be used as
an additional structural method for glasses. These
studies show abilities of using ICL for investigation
degree of polymerization of structure (NBOrr) of dif-
ferent silicate glasses.
[1] Neuville D.R. and Mysen B.O. (1996) Role alumi-

num in the silicate network: In situ, high-temperature
study of glasses and melts on the join SiO,-NaAIO,.
Geoch. and Cosmoch. Acta, 60, 10, 1727-1737. [2]
Mysen B.O. (1999) Structure and properties of mag-
matic liquids: From haplobasalt to haploandesite.
Geoch. and Cosmoch. Acta, 63, I, 95-112. [3]
McMillan P., WolfG.H., Poe B.T. (1992). Vibrational
spectroscopy of silicate liquids and glasses. Chern.
Geology, 96, 351-366. [4] McKeown D.A., Galeener
F.I., Brown G.E. (1984). Raman studies of Al coordi-
nation in silica-rich sodium aluminosilicate glasses
and some related minerals. J. Non-Crystalline Solids,
68,361-378
Investigating the oldest traces of life by AFMlConfocal Raman Spectroscopy:

applications for the analysis of martian rocks F. Foucher and F. Westall, Centre de Biophysique
Moleculaire, UPR CNRS 430 I, Orleans, France (frederic.foucher@cnrs-orleansJr)
The most ancient morphological and chemical traces additional compositional analyses are made using EDX
of life occur in rocks aged 3.5-3.3 Ga originating in the (Energy Dispersive X-ray spectroscopy) and synchrotron
Greenstone belts of Barberton in South Africa and the radiation, and carbon isotope ratio is measured.
Pilbara in Australia. The ancient microfossils are the sili- Figure I shows examples of Raman spectra from car-
cified remains of small microorganisms that inhabited the bonaceous material in 3.45-3.33 Ga-old sediments from
volcanic muds of seafloors and shallow water environ- the Pilbara in Australia (Figs. lA-D) and Barbenon in
ments [I, 2]. These muds represent excellent analogues South Africa (Fig. IE-F). These sediments contain the
for Noachian-aged volcanic sediments deposited in simi- silicified remains of colonies of chemolithotrophic mi-
lar environments (anaerobic, hydrothermally influenced) croorganisms that lived on volcanic materials, obtaining
on a more habitable and water-rich Mars [3, 4, 5, 6]. We their energy and nutrients from them.
are investigating the ancient biosignatures using a variety
of techniques, including optical, electronic and atomic
force microscopies, synchrotron radiation, nanoSIMS
and Raman and IR spectrometry.
One of the major problems associated with this kind
of research is establishing the biogenicity and syngenic-
ity of the microfossils: do they really represent the re- He '-..,_ _.:-
mains of microorganisms and, if so, are they syngenetic
with the fonnation of the sediment and not a later con- l (D.'r'---------;
tamination. High resolution microscopies among other
techniques are necessary for demonstrating the biogenic- I
ity of the silicified microfossils but these techniques re-
quire invasive sample preparation, such as acid etching.
Other, less invasive techniques, such as confocal Raman
Be':' -
(F.~----_--_
spectrometry will be invaluable in proving the syngenic-
ity of the structures since they can be analysed directly
within their mineral matrix. Furthermore, the possibil-
ity of mapping the carbonaceous microfossils in three-
dimensions within their mineral environment will pro-
vide additional infonnation regarding the mineralogical
context of the rock and therefore its origin.
The system used for the Raman analyses (WITec Al- Figure I: Optical observations and corresponding Ra-
phaSOO RA) allows relatively large scans of the surface man spectra of organic matter. (A) Cluster of organic
(several tens of cm 2 ) to be made so that the geological matter observed in the Pilbara thin section and (B) the
context can be mapped at a macroscopic scale. Car- associated Raman spectrum. (C) Large dark cloud of or-
bonaceous material of potential biological origin is first ganic matter observed in the Pilbara thin section and (D)
carefully localized in the thin sections and the variations the associated Raman spectrum. (E) Thin microbial mat
in the kerogen spectrum versus the different shapes and observed in the Barberton thin section and (F) the asso-
the surrounding minerals are studied by confocal Ra- ciated Raman spectrum.
man spectrometry. Since the individual fossils are sub-
micrometric, their visualisation requires high magnifica-
tion devices. The atomic force microscope (AFM) cou- From these data, it is clear that there are different
pled with the Raman microscope can thus image the fine phases of carbonaceous matter in the rocks. The car-
structure of the surface material. Complementary anal- bonaceous matter in all the samples is mature, as seen in
yses are carried out by scanning electron microscopy in the width and the ratio of the graphite and disorder peaks
order to observe the embedded microfossils after etching (1600 cm- 1 and 1350 cm- 1 respectively), and consis-
the rock surface. Finally, since the shape of the struc- tent with the age and metamorphic history of the rocks in
tures is not sufficient to demonstrate their biogenicity, which it occurs (lower greeenschist) and thus confirming
the syngenicity of the material. The well-defined clump

in Fig. lA is more mature than the diffuse cloud in Fig.
1C. The fonner may reflect reworked, older, more ma-
ture carbonaceous material whereas the latter probably
represents a colony of silicified chemolithotrophs on the
surface of a volcanic particle [2J. Likewise, the thin car-
bonaceous layers in the Barberton sediments present the
same kind of kerogen signature as found in cloud in Fig.
Ie.
Our results are of relevance for the search for fos-
silised traces of life on Mars. During the EXOMARS
mission, planned for 2016, the maximal resolution of the
microscope (MicrOmega) is 41lrn. These observations,
associated to the Raman analyses, could allow the de-
tection of carbonaceous matter and, although they will
not resolve the biogenicity of the materials, they will be
extremely imponant in deciding which rocks to sample
for detailed geochemical analysis of the organic matter
by GC-MS. Furthermore, combined optical and Raman
analyses will be essential in selecting suitable samples to
be returned to Earth in a Mars Sample Return mission.
References
[I] Westall, F. et aI., Implications of a 3.472-3.333 Gyr+old
subaerial microbial mat from the Barbenon greenstone
belt, South Africa for the UV environmental conditions
on the early Earth, (2006), Philosophical Transaction of
the Royal Sociery of London B, 361, 1857-1875.
[2] Westall, F. et aI., The 3.466 Ga "Kitty's Gap Chert", an
early Archean microbial ecosystem, (2006), Geological
Society ofAmerica, Special Paper 405, 105·131.
[3] Fassett, C. I., and Head ill, 1. W., Valley network-fed,
open~basin lakes on Mars: Distribution and implications
for Noachian surface and subsurface hydrology, (2008),
/carus, doi: 10.10 16.1j.icarus.2008.06.0l6.
[4] Brack, A., Why exobiology on Mars?, (1996), Planetary
and Space Science, 44, 1435-1440.
[5] Westall, F. et aI., An ESA study for the search for life on
Mars, (2000), Planetary and Space Science, 48,181-202.
[6] Walter, N. R., and des Marais, D. 1., Preservation of Bi-
ological Information in Thermal Spring Deposits: Devel-
oping a Strategy for the Search for Fossil Life on Mars,
(1993), /cams, 101, 129-143.
GATED LASER-BASED SPECTROSCOPY OF MINERALS: LUMINESCENCE, RAMAN, LIBS. M. Gaft'

'Laser Detect Systems (LDS), II Granit St., Petach Tikva 49514, Israel
Conventional CW (continuous-wave) spectroscopy is a The main problem for Raman effect is its weakness
process where the excitation sources pump the sample relatively to background luminescence. Gated Raman
at constant intensity over the time required to perform enables to overcome this because the Raman
the measurement. The end result is an emission or interaction time is virtually instantaneous, whereas
scattering spectrum, which in many cases is inadequate luminescence is slower, with minimum hundreds of
because limited discriminatory capability. picoseconds decay time. Our detection system is gated
Time-resolved luminescence spectroscopy utilizes the so as to detect only photons scattered or emitted during
fact that luminescence lifetime is a characteristic and a the laser pulse. Thus we will collect all of the Raman
unique property and it is highly improbable that two photons but reject the majority of the luminescence.
different luminescence emissions will have exactly the Consequently Raman and luminescence are separated
same decay time. The method involves recording the in time domain. Gated UV Raman technique gives
intensity in a specific time "window" at a given delay additional advantages. In the UV range with very
after the excitation pulse. Time-resolved luminescence energetic photons, the Raman lines are very close to
spectroscopy is extremely effective for studies of excitation, while in this spectral range the
minerals, many of which contain big amount of luminescence is very weak because of Stocks shift.
emission centers simultaneously. It enables to detect Thus Raman and luminescence are separated in
weak luminescence centers, which remain unnoticed in spectral domain. Besides, UV Ramf cross section is
CW spectra. The mostly known examples are apatite, enhanced strongly because of (l/A) dependence and
zircon, calcite, fluorite [1]. Figure I demonstrates the even much higher at the vicinity of allowed electronic
corresponding spectra of diamonds, where several transitions. Figure 2 demonstrates UV gated Raman
luminescence centers may be detected by time-resolved ability, using Terlingua-type calcite, where Raman
technique under N3 luminescence detected by CWo lines covered by luminescence in CW spectra may be
detected. Enather example (Fig. 3) is differentiation
between Raman lines and narrow luminescence lines of
,; 0=200 ns REE'· by gated Raman technique [2].
,i100 G=500 os
.
?:
~ 50
.
,
,.
•....
I.M a355 nlll ~o ns
~
£ •
400 500 600
""
~ 150
~
?:
.~ 100
c 70
60
~oo c
1055
l..._365 nm
0",..10n•
While
."
"" " . '00'
Pln~
1.".266nm
•
£
0":10n•
so "' ,,.
50 1"-~-=r-=""r----..J
..
,~
,,~
400 400 500 600

;- 100 .r----'-..:,~.., , =
Ram.nshlft,cm~
.i 30
::: 80
.;;
o
Figure 2. Short-lived violet luminescence spectrum (A"
.E• 60
= 355 nm) of radiation-induced center in Terlingua-
type calcite and its decay as a function of delay time
400 500 600 500 600 700
(a), gated Raman spectra (A" = 355 nm) in pink (b)
nm nm
and white (c) varieties, and gated Raman spectra (A" =
Figure 1. Laser·induced time-resolved luminescence 266 nm) in pink variety (d). RamanlLuminescence ratio
spectra of diamond (A..~355 nm, 300 K, D-delay, G- may be improved by deep UV gated Raman technique
gate). Only N3 luminescence center is detected by CW because of spectral separation of Raman and lumines-
luminescence cence signals.
'" M'
'" M'~
'" M' "'. '" ~ troscopies are complementary techniques and their
:
,~
~ •, ,, , '" , .
CollllnUOUf Wave ,~
S77 11m
~~
57~
~
11m instrumentation is quite similar. A UV laser is used for
exciting the sample, the light is collected from the
.,
· ..
< ,
;;, '00
•
-. "'. . ·•. •
• < • < '00 sample, is dispersed using a visible or UV grating mo-
~. • Ci~
] ~ nochromator, and its spectrum is measured with an
..
~~ ~;
00
; ColltinUOUf w_
oo array detector, usually an ICCD.
"'" ,
,.. ,..
'''''' "'" , '''''' Luminescence may be especially useful in detection of
:
€
oo
~
~
• Ga_1Gnf
200
so-called pathfinder minerals such as calcite, apatite,
barite, and fluorite. These minerals presence may be
related to the processes of differentiation of some ore
i
5 . \.Zo ". forming elements and their accumulation in local struc-
,..
tural and geomorphological traps. The accumulation of
,.. "'" '00' ''''''
,.. luminescent substances in separate sites of the Earth
"'" ''''''
Ramall Shitl, <;:m~ Raman Shin, <;:m~
crust is the result of concentration of rare and ore ele-
ments. The are elements give mineralogical and geo-
Figure 3. CW (a,b) and gated (c,d) Raman spectra (A" chemical anomalies that can be used in searching for
= 532 nm) of titanite and rhodonite, respectively. The ore bodies [5]. Besides, luminescence technique
titanite lines at 600, 579, 575, 564 and 558 om visible enables detection of other natural objects, such as fo-
only in CW spectra belong to Sm3+, Dy'+ and Eu3+ lu- liage, always characterized by very characteristic chlo-
minescence. Rhodonite lines visible only with a broad rophyll luminescence with very short decay time (Fig.
gate occur at 577, 579 and 545 nm and are connected 4).
with Dy+ and Tb 3+ luminescence.
In Laser Induced Breakdown Spectroscopy (LIBS), the

plasma light created by laser is analyzed to determine
the elemental composition of the sample. Plasma
emission can be divided into two time domains. The
first one is characterized by a broad emission HG toO &60 7QC1 no toO
originating from the Bremsstrahlung of the free
electrons and electron·ion recombination and it has
duration of a fe~ hundred nanoseconds. The second
time domain is characterized by an emission spectrum,
where narrow atomic lines dominate corresponding to
the elements present in the plume and the line strength
$50 .00 .50 700 7M .00
is proportional to the atomic concentration. This time
regime lasts for several microseconds, where in its
early stage ionic lines are strong, while the atomic lines Figure 4. Chlorophyll laser-induced luminescence in
dominate later on. From the temporal behavior of foliage
plasma, it is clear that the identification has to be done
by time-resolved spectroscopy, that is, the delay and References
the gate in respect to the laser pulse have to be [I] Gaft M. et al. (2005) Modern luminescence spe<;tros-
optimized to maximize the informative line spectrum copy ofminerals and materillls. Springer, Berlin Heidel-
and avoid the early part of the signal, corresponding to berg New York, 350 p.
the strong unstructured continuum. [2] Gaft M. and Nagli L. (2009) Gated Raman spec-
Combination of visible Raman and LIES techniques troscopy: potential for fundamental and applied mine-
has been proposed for remote detection of minerals for ralogy, European Mineralogical J(in press)
planetary applications [3, 4]. By analyzing the cation [3] Misra A. et al. (2006) Detection of water and water
information collected in the LIBS experiment along- bearing minerals from 10m distance under bright con-
side the anion infonnation provided by gated Raman ditions using remote Raman system. Lun. Planet. Sci.,
scattering, a more complete image of the mineral's 37,2155.
structure and composition can be obtained. The inte- [4] Sharma S. et al. (2003) Stand-offRaman spectros-
gration of UV Raman, time-resolved luminescence and copic detection ofminerals on planetary surfaces.
LiBS enables even more sophisticated tool for both Spectrochim. Acta, A 59, 2391-2407.
detection and identification of minerals. All those spec- [5] Gorobets B. and Rogojine A. (2001) Luminescent
spectra afminerals. Handbook, RPC VIMS, Moscow.
32 LP/ Contribution No. 1473
SPECTRALLY-RESOLVED LUMINESCENCE OF MOGANITE FROM MOGAN (GRA 'CANARIA)

J. Garcia-Guinea 1,· M.A. Bustillo'., E. Crespo-Feo!, A.A. Finch 2, P. D. Townsend), D. E. Hole), L. V. Correcher4 .
IMuseo Nacional Ciencias aturales-CSIC, Jose Gutierrez Abascal 2, Madrid 28006, Spain,
abustillo@mncn.csic.es; 2Centre for Advanced Materials, University St Andrews, Irvine Building, St Andrews, Fife,
KYl6 9AL, UK, 'Science and Technology, University of Sussex, Brighton, BNI 9QH, UK., 'CIEMAT. Av. Com-
plutense 22, Madrid 28040, Spain.
Introduction: Moganite mineral (SiO,) was initially corded at 10 degree intervals during cooling ITom
found in a near pure form in the locality-type of room temperature down to 40 K [4].
Mogan (Gran Canaria) [1], it was accepted as a poly-
morph of silica at 1999 (IMA N' 99-035). The mogan- Results and Discussion: Raman plots facilitates the
ite intergrowth within microcrystalline silica phases selection of moganite-rich zones for further U, RL
exhibits a widespread distribution at the Earth's sur- and ffiL analyses. Figure I shows two spectra taken
face. [2]. This silica polimorph contains as much as 4.5 ITom an hyperspectral plot, straight-line belongs to a
wt.% H,O, and 0.5 wt.% CO,. Raman spectroscopy mixed zone in where quartz (465 cm-') is more intense
technique provides a measure of the moganite content than moganite (502 cm· l ) and dotted-line is moganite
in sample and its spatial variation [3]. Luminescence richer, as the case of previous spectra CL of Mogan
techniques are increasingly employed on natural silica moganite specimens [3].
[4], hence, it is essential to examinate luminescence
spectra emissions of silica aliquots, at different tem- 220 moganite quartz
peratures under different excitation agents, i.e.., here, -; 180 • !\
protons for ion beam luminescence (ffiL), x-
irradiation for radioluminescence (RL) and heating for
~ 160 hI
thermoluminescence (TL), to link defects and spectra ~ 100 \
luminescence emissions. ai
c:
60
20
\
.r
Experimental: We study well·characterized mogan-
ite-type specimens collected by author M.A.Bustillo
600 560 520 480 440 400
from fissures of rhyolitic ignimbrite flows in Mogan
(Gran Canaria) [5]. Moganite rich aliquots were se- Raman shift (cm-1 )
lected by hyperspectral Raman using a new Ther- The results of the EPMA spot analysis of moganite
moFischer Raman Microscope with one micron spatial samples shown in Table I do not include molecular
resolution and a laser source at 532 run. The Electron water, hydroxyl groups, CO, and CO previously re-
Probe Microanalyses (EPMA) of samples were per- ported [6] in maganite samples, which can be extrapo-
formed by a leal Superprobe JXA-8900M and by En- lated up -5% of pure maganite to close the EPMA
vironmental Scanning Electron Microscopy with X-ray analyses. These authors reported weight losses ranges
Dispersive Spectrometry probe (ESEM-EDS) in a In- from 0.16% to 4.60%, increasing with the moganite
spect-S ESEM of the FEI company. TL measurements content [6]. Table I: Experimental EMPA analyses of
of moganite were performed using an automated Rise Moganite samples performed in this work.
TL system model TL DA-12 with an EM! 9635 QA
photomultiplier and a blue filter Fffi002 in which the SiO, 94.16 95.04 94.61 94.75 94.82
wavelength is peaked at 320-480 nm. Spectra RL AI,O, 0.28 0.38 0.01 0.24 0.80
emissions were recorded in the high sensitivity spec- FeO 0.01 0.00 0.06 0.02 0.07
trometer of the University of Sussex, over the 200-800 MnO 0.03 0.02 0.00 0.00 0.00
nm wavelength range during excitation of samples MgO 0.06 0.05 0.01 0.05 0.08
with 50 Gy X-irradiated employing a Phillips MG CaO 0.09 0.07 0.04 0.03 0.12
MCN 101 X-ray tube with a current of 15mA and a Na,O 0.09 0.09 0.06 0.06 0.13
voltage of 25 kV. The ffiL was performed under vac- K,O 0.03 0.07 0.02 0.02 0.11
uum using the 3.0MeV Van der Graff accelerator facil- TiO, 0.00 0.03 0.01 0.02 0.00
ity at the University of Sussex generating a spot size of NiO 0.01 0.02 0.01 0.00 0.00
-0.25 cm 2• The ion beam has a 45° offset between Cr,O, 0.00 0.00 0.00 0.00 0.04
beam incidence and viewing angle. Light is trans- P,O, 0.00 0.01 0.02 0.01 0.02
ported by a silica fibre to a spectrometer with a cooled CI 0.10 0.14 0.09 0.12 0.07
CCD camera. Temperature is controlled and data re- Total 94.86 95.92 94.94 95.32 96.26
Figure 2a shows a TL glow curve at wavelength 320-

~
6000
12/a--lmab
phase transition
at 570 K
® 480 nm of a selected fresh moganite aliquot. The TL
light emission centres must be compatible with the
:::> 5000
~ TL volatile loss, Le., water, hydroxyl groups, CO 2 and CO
~ 4000 glow gases, occurred as a two steps process, with high loss
:!! 3000 TG curve rates first between 323 and 453 K and then between
~ step-1 553 and 823 K, previously reported in thermochemis-
c 2000
try papers on moganite-type [6]. In addition, the
1000 reversible phase transition from space group i21a to
Irnab at approximately 570 K [7] is located in the
o maximum of TL light emission. Figure 2b depicts a
200 300 400 500 600 700 800 spectra 3D RL plot of moganite-type recorded, from
Temperature (K) RT to 40K, in the high sensitivity spectrometer of the
Sussex University. In accordance with the EPMA
analyses and the observed spectral RL broad band,
moganite seems include many of the emission-defects
catalogued for SiO, [8], e.g., 470-500nm [AlO,]' cen-
ters, 580nm Oxygen vacancy, 620-650nm Non-
bridging oxygen ions; 700nm Substitutional FeH . Dur-
ing the RL measurements (Fig 1b) the lattice cryogenic
stress enlarges progressively the RL emission pointing
€...-
to structural defects linked with bond-breakings, and
6¢0.s;
<>'0
VV:. "if0 0
&#
~# probably, with a continuous reduction in the b axis and
<9.....& /& "if0 0
:?Ul'''''' 3<>0 ~~ the concomitant rotation of tetrahedra about [100] [7].
("/)'J'}..,J <...;to Figure 2c depicts IBL profiles ofmoganite from RT to
80 K with spectra positions at circa 400nm, 500nm and
~
7000 80 K © 700nm. In this case, the progressive cryogenic stress of
the lattice enlarges also the ionoluminescence emission
::i 6000 120 K with a similar behaviour. Furthennore, figure 2d
2- 5000 160 K shows and initial IBL profile at RT using J-t ions and a
~ final profile after a sequential series of twenty IBL
'0; 4000 200 K
c profiles at RT. This final profile shifts clearly towards
Q) 3000 240 K the red/orange region during implantation since the
:£ 2000 280 K dose dependence of the red/infrared emission as a
1000 320 K function of integral dose. This peak shift can be ex-
plained in tenns of changes to the coordination sphere
0
of the activator Fe3+ ion caused by the ion bombard-
200 400 600 800 1000 ment [9].
Wavelength (nm)
References: [1] O.W. FlOrke et aJ. (1976) Zeit. Krist.
~
7000 @ 143, 156--165, [2] PJ. Heaney and J.E. Post (1992)
Science 255, 441-443, [3] J. Gotze, L. et aJ. (1998)
:::> 6000
Conlr. Miner. Petrol. 133, 96-105, [4] T. Moxon and
~ 5000
S. J. B. Reed (2006) Miner. Mag 70, 485-498, [5]
~
'0; 4000 M.A. Bustillo. J Iberian Oeol. 28, 157-166, [6] I. Pet-
c rovic et aJ. (1996) Phys Chern Miner. 23: 119-126, [7]
~ 3000
c Heaney, PJ. and Post, J.E (2001) Arner Miner. 86,
2000
1358-1366, [8] M.R. Krbetschek et aJ. (1997) Radial.
1000 Meas. 27, 695-748, [9] A. A. Finch et aJ. (2003) Phys.
0 Chern. Mineral. 30,373-381.
200 400 600 Acknowledgements. Supported by the project CGL-
800 1000
20008-05584-C02-01 and Contract CSIC JAE-DOC
Wavelength (nm)
34 LPf Contribution No. 1473
THE QUARTZOFELDSPATIllC FULGURITE OF BUSTAVIEJO (MADRID): GLASSY MATRIX AND

SILICON PHASES. J. Garcia-Guinea!, M. Furio!, M. Fernandez-Hernan', M.A. Bustillo', E. Crespo-Feo', V. Co-
rrccher 2, L. Sanchez-Munoi and E, Matesanr, lMuseo acional Ciencias Naturales-CSIC, Jose Gutierrez Abascal
2, Madrid 28006, Spain, 'CIEMAT, Avenida Complutense 22, Madrid 28040, Spain. 'Centro de Apoyo a la lnves-
tigacion de DRX. Univ. Complutense Madrid. 28040, Spain. Correspondence author: mfurio@mncn.csic.es
Introduction: Fulgurites are glassy irregular tubes Microscopy with X-ray Dispersive Spectrometry probe
produced by the fusion of sand, which has been struck (ESEM-EDS) in an Inspect-S ESEM of the FEl Com-
by lightning. They have attracted attention from very pany. The in situ high-temperature X·ray diffraction
early times, e.g. in Spain a fulgurite was described and (HTXRD) fulgurite patterns were recorded from rocm
outlined (Fig. I), in the XlI Century, at 1250, in the temperature (RT) to I200'C using a Panalytical X-Pert
medieval book, Lapidary of King Alfonso X The PRO MPD diffractometer (Cu Kn radiation, 45 kV, 40
Learned [I], kept in the Esoorial monastery main li- rnA) equipped with a high-temperature Anton Paar
brary, as the stone number 206, labelled mazintarin- HTKl200 camera and a fast detector X'Celerator with
can, i.e., an ancient Chaldean tenn. Ni ~ filter. During circa 17 h, we performed 76
HTXRD profiles from RT to 1200'C, with gaps of
:\'ltUlll qUt.*11.0111lnC41,~ltfitt:U41n lO'C/min berween each XRD pro-file. The Thermolu-
minescence (TL) measurements of fulgurite were per-
~~gmt'" formed using an automated Risa TL system model TL
DA-12 with an EMI 9635 QA photomultiplier. The
ttO\t~ emission was observed through a blue filter FIB002 in
lA~a4U4 which the wavelength is peaked at 320480 nm. The
•.
~.-a-
...
;"
Fig.I. Image offulgurites from Lapidary book of King

hyperspectral Raman quartz and cristobalite distribu-
tion was explored with a ThermoFischer Raman Mi-
croscope which has a point-and-shoot Raman capabil-
ity of one micron spatial resolution using a laser source
at 532 nm.
Results and Discussion: The Bustarviejo fulgurite
is made of alumino-silicate glass, shocked quartz, and
Alfonso X. neo-formed cristobalite. The sphaeroidal vugs, sized
The pioneer publication of Myers & Peck at 1925 from micron to centimeter, exhibits black spot of na-
[2] on the sand-claystone fulgurite of South Amboy tive Si-Fe-Al alloys, with different ratios, which un-
(New Jersey, USA) describes quartz centers sur- mixed from an alumino-silica-rich melt. (Fig. 2).
rounded with a fine grained border of cristobalite and
black stained areas attributed to possible iron oxides.
The extreme reduction produced by lightning strike
fusion and the discovery of silicon and silicon-iron
alloys was later described in natural fulgurites [3-4].
Additional findings of fulgurites from other rocks were
also studied with luminescence and stable isotopes
techniques [5-8]. Here we studied the fulgurite com-
ponents by both, classic and modern spectral and elec-
tron microcopy techniques to learn more on the differ-
ent silicon phases.
Fulgurite samples and experimental: We found,
and study, a glassy quartzofeldspathic fulgurite,
formed .recently on arkose sediment which covers
granite rock of Bustarviejo village (Madrid, Spain).
Quartzofeldspathic fulgurites formed from arkosic
sediments are highly vesicular but does not develop
pipelike shapes as the case of those formed in only
quartz sands. The Electron Probe Microanalyses Fig.2. Images of fulgurite fragments a) and section.
(EPMA) were performed in a Jeol Superprobe JXA- ESEM images of a quartz crystal morphology c), and
8900M and also by Environmental Scanning Electron Fe-Si-AI alloys d).
Conference on Micro·Raman Spectroscopy and Luminescence Studies 35
The EPMA analyses of glasses display the following

Quartz
• @ compositional ranges ('Yo): SiO, (63-70.68), AI,O,

~~ ,~~
~
2l
(19.00-23.63), FeO (0.06-2.09), CaO (0.04-0.74),
Na,O (0.03-0.17), K,O (0.09--D.96), P,05 (0.01-
•
It i~~~~p !I ~
.~
~ ~ 0.016) as the most representative elements. The top

~ .;;;.¥ 0 ::l 0
•,
0 analyzed amount CaO (0.74) and Na,O (0.17) stern
" 00
w,~
0 I I from the same sample, i.e., a single former grain of
plagioclase. The thermal variations of low quartz and
10· 2()0 30" 4QO 50" 60" low cristobalite were observed by HTXR.D. At circa
29 angle 247°C, the low-high cristobalite phase transition oc-
curs; at 540"C the low-high quartz and finally heyond
o
o
r Position (microns)
-3300 -3250 -3200
1l00"C the quartz peak at 26,47 20 splits arising a lit·
tle peak which disappears beyond I 180"C. The ex·
perimental TL glow curve of the fulgurite is composed
hy a broad hand peaked at 233"C--123a.u. and two
co peaks at 460"C--500a.u. and 494"C-1500 a.u., unfor·
....
co
I
tunately, these values do not allow us to perform TL
dating since the surrounding sediment. i.e., quartz plus
o alkali feldspars display a huge TL emission peak at
10 223"C-571 000 a.u. and 274"C - 417 000 a.u., only
co
co
....
I
let us to conflrm that it is a geologically recent strike
older than circa 30 years which is the time being ob-
served by the surrounding population. The main part
o~ii!iii
(") of the glassy matrix exhibits a molecular-Raman struc-
co ture similar to a synthetic gel of potassium alumino-
....
co
I
silicate obtained experimentally via sol-gel. The hy-
perspectral Raman contour plots of quanz grains out-
~ line its cristobalite outer comparing characteristic
co maxima peaks at 465 ern'] (Quartz) and 415 ern'] (Cris-
co
...., tobalite) (Fig. 3). Both data, i.e., spot of plagioclasic
glass and cristobalitic boundaries of the inlaid quartz
o grains, let us to infer on the short time lightning strike.
10
co This fulgurite sized 12 cm in diameter in the main
....
co
I
branch, was formed by lightning strike fusion on ar-
kosic sand during a fast process of volatilization and
L -3270 -3260 -3250

Position (microns) •
extreme reducing conditions at temperatures in excess
of2000 K [4].
References: [I] Alfonso X El Sabia (1250) EI La·
pidario. Book. Esc. Trad. Toledo. Spain. Issue in EI
Quartz,
© Escorial monastery library. [2] Myers W.M. and Peck
A.B. (1925) Amer. Miner. 10, 152-155. [3] Blaschke
cristobaliti R. and Pfefferkorn G. (19g3) Forrschr. Miner 61, 27.
,/ '
[4] Essene EJ. and Fisher D.C. (1986) Science, 234,
Q I "
,, A
189-193. [5] Ablesimov N.E. et al. (1986) DokJ. Akad
B i • .A.
Nauk 290, 1454-1458. [6] Appel P.W.U. et al. (2006)
Geol. Mag. 143, 737-741. [7] Navarro-Gonzalez R. et
al. (2007) Geology 35, 171-174. [8] Champagnon B.
C JV\ et al. (1997) Chern. Erde Geochem. 57,290-296.
Acknowledgements. Supported by the project
500 400 300 200 100 CGL-20008-05584-C02-01, and a JAE-Doc CSIC
Raman shift (em-') contract.
Fig.3. a) Fulgurite XRD diffractogram; b) hyperspec-
trally analysed area; c) 2D Raman map; and d) Raman
spectra of marked points in Fig.2c.
Spectra Cathodoluminescence and Raman Imaging of Na-rich Feldspar and Maskelynite from The Villalbeto
de la Peoa Meteorite. J. Garcia-Guinea l , L. Sanchez-Mufioz2, L. Tormol, E. Crespo-Feo l , J. Ruiz), A. I. Martin-
Herrero\ A. Cremades), IMuseo Nacional Ciencias Naturales, Jose Gutierrez Abaseal 2, Madrid 28006, Spain.
'CIEMAT. Av. Complutense 22, Madrid 28040, Spain. 'Centro de Biologia Molecular, CSIC-Universidad Aut6no-
rna de Madrid, 28049 Cantoblanco, Madrid, Spain. 4Seminario de Ciencias Planetarias, Universidad Complutense
de Madrid, 28040 Madrid, Spain. SDpto Fisica Materiales, Facultad de Fisicas, Universidad Complutense de Ma-
drid. 28040 Madrid. Spain. Correspondence author: l.tormo@mncn.csic.es
Introduction: The fall of the Villalbeto de la Pena spot analysis on feldspar phases are shown in both,
meteorite on January 4, 2004 (Spain) is one of the best Table 1. as some representative analyses of feldspar,
documented in history for which atmospheric and or- and Figure 1. which displays the ternary Na2Q-
bital trajectory, strewn field area, and recovery circum- K,o-CaO compositions of Villalbeto feldespathic
stances have been describ~d in detail [1-2]. Additional samples.
details on the bulk chemistry [3] and the bulk lumines- Bytow. Albi!. Oligo. Mask. Mask.
cence [4] were later provided. Moreover, the intrinsic SiO, 64.63 64.87 66.15 67.84 68.81
complexity of composition, distribution and structural AI,O, 17.58 21.18 22.87 23.28 22.96
states of plagioclase crystals in L6 chondritic meteor- FeO IAI OA4 0.54 0.31 0.66
ites [5], such as the Villalbeto feldspars case, sug- MnO 0.01 0.00 0.08 0.00 0.00
gested us to perform this study by Electron Probe Mi- MgO 3.76 0.01 0.02 0.00 0.03
croanalyses (EPMA), spatially-resolved spectra Ca- CaO 8.20 2.36 2.51 2.24 2.16
thodoluminescence (CL) and HyperspectraI-Rarnan Na,O 2.75 9.91 6.87 3.99 2.67
contour-plot micro-analyses (Raman), exploring the K,O 1.14 0.27 0.66 1.82 1.71
Maskelynite-Plagioclase distribution of thr studied TiO, 0.10 0.00 0.02 0.01 0.09
samples. NiO 0.03 0.01 0.00 0.00 0.10
Cr203 0.15 0.00 0.00 0.00 0.02
Experimental: We study polished sections of L6- P,O, 0.Q3 0.02 0.03 0.00 0.00
chondrite specimens collected by ourselves in Villal- Total 99.79 99.07 99.75 99A9 99.21
beto (Palencia). The Electron Probe Microanalyses
(EPMA) were performed by a Jeol Superprobe JXA-
8900M and by Environmental Scanning Electron Mi-
croscopy with X-ray Dispersive Spectrometry probe
(ESEM-EOS) in a Inspect-S FEI company. Transmis-
sion electron microscopy (TEM micrographs and se-
lected area electron diffraction (SAEO) were obtained t' \,
with a Tecnai20T (PHILIPS) microscope working at
200 kV. The hyperspectral Raman contour plots were
4:-~ O·50I'----~~o .-t--\; 0.50 \
0-
• 0
perforned using a new ThermoFischer Raman Micro-
scope and a laser source at 532 nm. The hot cathodo· 0.75 .maskelynitic 0.25
luminescence (CL) spectra were obtained with an couplings
SEM-CL Hitachi S2500 electron microscope and a
Harnamatsu PMA-I 1 CCO camera. Cold CL images of 1.oo'c-_--:-:::-_=,-_=_ _:-' 0.00
0.00 0.25 0.50 0.Tl5 1.00
VillalbelO feldspars distribution were taken in a optical CoO(Wt%)
CL 8200 MK4 system of Cambridge Image Technol-
ogy Ltd. Na-rich feldspars were analyzed by transmission elec·
tron diffraction (TEM) and selected area electron dif-
Results and Discusi6n: From the intensity of blue fraction (SAED) along [001] zone axis, in a micro-
CL and BSE contrast in SEM images (Fig. 2a and b), scope with an EDAX facility to correlate chemical,
two different regions of feldspatic composition have structural and microstructural data. No twinning were
been observed: i) Maskelenite and Na-rich feldspars identified in TEM images, diffraction spots do not
forming mixtures at a level lower than the resolution of show splitting. and a regular circular shape allow us to
optical microscopy techniques forming like-veins be- measure the y* angle being lower than 90°, indicating
tween other crystals and intergrowths with pyroxene~ a high or intermediate albite local ordering scheme in
ii) extended volumes with homogeneous Na-rich feld- the SiiAI distribution. Maskelynite was easily identi-
spar crystalline structure. The results of the EPMA 45
tied by the lack of structure in the electron diffraction tions, as follows: (i) red spots, Bytownite with Mn'+
spectra. From our experimental results we infer that point defects in structural Ca positions, (ii) blue
the metastable proportional K-Ca-Na compositions, masses, Oligoclase with [AI04]" defects, (iii) Mas-
sited in the triangle center, could be partially amor- kelenite sodic glasses with low UV-blue emission.
phous Maskelynite, together with plagioclase species, Figure 2b&c displays the spatially-resolved hot CL
e.g., Bytownite, Albite, Oligoclase (Table 1). spectra taken on the feldspar masses observed by
ESEM matching with the cold CL picture. A Hyper-
spectral Raman plot was perfonned to explore the pla-
gioclase crystal (Fig.3). The Maskeline amorphous
phase was mainly observed in the Plagioclase fissures.
X~ LJ
3500 3000 2500 2000 1500 1000 500
Raman shift (cm-1)
The Maskelenite Raman spectrum includes com-
mon peaks with plagioclases phases. This datum point
30
1W .~~~
Mask to a tectonic origin for this, in accordance with previo-
ous data reported indicating that Villalbeto meteorite
li~~;~~~~~M~a~sk~
20 was not severely shok-metamorphosed [3]
as
10 References: [I] L10rca J. et aI. (2005) Meteoritics

Oligoclase & Planet. Sci., 40, 795-804. [2] Trigo-Rodriguez J.M.
et al. (2006) Meteoritics & Planet. Sci., 41, 505-517.
300 <400 500 600 700 800
[3] L10rca J. et al. (2007) ) Meteoritics & Planet. Sci.,
Wavelength (nm) 41. AI77-AI82. [4] Correcher V. et al. (2007) NIM
Phys Res. A. 580, 637-640. [5] akamura., Y. and Mo-
The meteorite luminescence is mainly produced by lomura., Y. (1999) Meteoritics & Planet. Sci.. 34. 763-
feldspars, Figure 2a shows its cold CL plot distribu- 772.
CATHODOLUMINESCENCE OF LUNAR MINERALS AND ROCKS. J. Gotze' , 'TU Bergakademie Frei·

berg, Institue of Mineralogy, Brennhausgasse 14, D-09596 Freiberg, Germany; goetze@mineral.tu-freiberg.de.
Introduction: The results of geophysical meas- which were observed in meteorites, have not been de-
urements and investigatios of geological material indi- tected in lunar samples up to now [3].
cate that the internal structure of the Moon is similar to Feldspar minerals. Plagioclase is the dominant lu-
that of the Earth and consists of a core, a differentiated minescent mineral in lunar rocks and breccias, whereas
mantle and a thin crust (-60 km) [I]. The lunar crust alkali feldspar is only a minor component especially in
consists in general of three main rock types: (1) anor- more acidic lithic fragments [4]. These alkali feldspar
thosites and anorthositic gabbros (ANT suite), (2) ba- grains with a compositional range of Orn.ssAbls.2sAno_
salts rich in K, REE, P, Zr, Ba and U (KREEP basalts), 1 in general exhibited a bright blue CL, similar to that
and (3) basalts rich in Fe and Ti (FETI suite) [2]. In of terrestrial feldspars. The alkali feldspars contain up
addition, the appearance of the recent lunar surface can to 0.6 wt.-% Ba and show mostly a broad emission
be related to the formation and alteration of a thick (up band in the blue consisting of two overlapping emis-
to 10 km) regolith cover during the last 3.0 Ga. Due to sions at ca. 450 nm and 500 nm, respectively. Another
the lack of an atmosphere and water, no weathering or type of luminescent alkali feldspar was found in fine-
sedimentation processes occur on the moon and the grained lithic fragments of Luna 20 material, where the
exogenic processes are restricted to the ongoing bom- yellow-olive luminescent feldspar is intergrown with
bardment by cosmic material resulting in the formation SiOz. The CL spectrum shows two emission bands at
of large crater regions and the destruction (and par- -450 nm and 700 nm. In contrast to the Luna 16 sam-
tially melting) ofrocks [I]. ples, the 500 nm emission is absent and the alkali feld-
Lunar Minerals: The mineral composition of lu- spar contains no detectable Ba but 0.62 wt.-% iron.
nar rocks is much simpler than that of terrestrial rocks. The pronounced red emission is the evidence that at
Plagioclase is the most abundant mineral of the high- least some of the iron is Fe3+ incorporated in the Ae+
land rocks (enriched in Ca and AI), whereas pyroxene, lattice position. A blue luminescent feldspar grain with
plagioclase and ilmenite dominate the mare basalts the uncommon composition Or54AbjAn4s was detected
(pyroxene together with plagioclase 75-90%). Olivine in a lunar breccia of Luna 16 [3].
and the high-temperature silica modifications tridymite The visible luminescence of plagioclase shows a
and cristobalite mostly occur in contents between 1 wide range of intensity and colour ranging from pale
and 10% [2]. A couple of accessory phases were found blue to green. Many of the crystals appear more or less
in lunar rocks such as the silicates pyroxferroite homogeneous under CL, others show zoning or irregular
(Ca,Fe)(Fe,MnMSi,02l] and tranquillityite areas with slightly different CL colours, which are not
Fe8Til[Zr,YJz[0I2/(Si04h], the Zr-minerals zircon discemable with other microscopic techniques. Lath-
(ZrSi0 4) and baddeleyite (zrO,), the phosphates apa- shaped crystals often exhibit a brightly greenish lumi-
tite (Ca,[(F,CI)/(P0 4 )lJ - OH free) and whitlockite nescent central part, whereas the rims are dull lumi-
(Cal(P04),) or monazite [2]. Moreover, the regolith of nescent. This zoning is often correlated with a chemi-
the lunar surface contains also high amounts of glassy cal trend from An-rich crystal cores to more albitic
particles, which may derive from either volcanic ac- rims, which can be related to preferential partitioning
tivities or from the melting of target material during of activator ions (e.g. Mnz+) in the crystallizing plagio-
impact events. clase, so that they become impoverished in the melt
CL of lunar minerals: In view of the potential during proceeding crystallization. Spectral analysis of
luminescence behaviour, the general high iron content the CL emission revealed that the lunar plagioc1ases
of most lunar material prevents luminescence activa- show in general three main CL emission bands in the
tion. Therefore, only a few, more or less iron-free min- blue around 450 nm (Al-O--Al centre), in the green at
erals have to be considered within the group of lumi- -560 nm (Mn'') and in the redIIR at -690 nm (Fe3').
nescent minerals. Calcic plagioclase, the silica modifi- Shock damage of plagioclase grains due to impact
cations tridymite and cristobalite, and traces of alkali events is detectable by features of brecciation and in-
feldspar are the dominant luminescent minerals in lu- ternal fragmentation up to the isotropization of plagio-
nar crystalline rocks and breccias. Some additional clase and the formation ofmaskelynite (Fig. 1).
accessory minerals have to be considered in respect to
their luminescence behaviour, among them the Zr-
minerals zircon and baddeleyite, and the phosphates
apatite and whitlockite. Other luminescent minerals,
emission spectra of crystalline quartz from terrestrial

rocks. Small, anhedral quartz crystals often show ir-
regular internal structures under CL, which are not
discernable with conventional microscopy (Fig. 2).
The comparison of the CL spectra of grain-areas with
different luminescence intensity revealed that the blue
band is relatively constant, whereas the bright areas
show a much more intense emission band in the red.
Calcium phosphates. Among the minerals of the
phosphate group, OH-free apatite and whitlockite
(general formula Cat,(Y,REEj,(Mg,Fe),(PO,)t,) occur
as accessory constituents of lunar KREEP rocks [4J.
The CL spectra of whitloekite (merrillite) are domi-
nated by strong emission peaks of several rare earth
Fig. 1 OM-eL image of a strongly brecciated plagic1as elements (Fig. 3).
grain fragment intergrown with pyroxene (px) from
the coarse fraction of Luna 20 regolith. 600 . , - - - - - - - - - - - - - - - - - - ,
Nd~+
Silica modifications. Because of their structural dif- soo

ferences, the silica modifications exhibit different lu- VI
minescence properties and thus, are distinguishable by 'E, 400
o
CL in lunar material [3, 4]. Tridymite is often inter- u
.... 300
grown with plagioclase in coarse-grained rocks and ~
shows a bright blue luminescence. The CL emission •
o
.! 200
spectrum of tridymite is dominated by a broad band .5
centred at ca. 500 nm. 'Cristobalite exhibits a dark blue 100
CL with a much less luminescence intensity compared
to that of tridymite, but a similar emission spectrum. o./--~-~-~-~-~-~
Quartz is absent in coarse-grained lunar rocks, but was 300 '00 500 600 700 800 900
reported from fine-grained rocks of Apollo 11 and 12 wavelength [nm]
[4], as well as Luna 16 and 20 [3]. In general, dull blue
and/or pink luminescent quartz was detected together Fig. 3 CL emission spectrum of whitlockite from Luna
with alkali feldspar or plagioclase (Fig. 2). 16, dominated by strong peaks of the REE ions [3].
Other phases. Most lunar samples contain glass of

different types. Because of the general high iron con-
tent, most of the glass fragments are non-luminescent.
However, bright blue, dark blue and reddish lumines-
cent glasses were detected, which mostly show silica
or feldspar composition [4]. Certain minerals, which
are known from meteorites, haven't been detected in
lunar samples up to now. 1t can not be excluded that
these minerals exist on the moon. Therefore, low iron-
bearing or iron free end members of the pyroxene or
garnet group, of olivine (forsterite) or spinel could be
potential minerals with usable luminescence proper-
ties.
Fig. 2 SEM-CL image ofK-feldspar/silica intergrowth
References: [I] Taylor S.R. (1982) Planetary sci-
in a fragment from Luna 20 soil; the heterogeneous
internal CL structure of silica is only visible under CL ence: a Junar perspective, LPI Houston. [2] Smith J.V.
and is caused by the varying intensity of the 650 nm (1974) Arner. Miner., 59,231-24. [3] Gotze J. (2008)
emission band. CL microscopy and spectroscopy of lunar rocks and
minerals, Springer. [4J Sippel R.F. and Spencer A.S.
The CL emission spectrum consists of two broad (1970) Proe. Apollo II Lunar Sci Conf., 3, 2413-2426.
bands with maxima at 420 and 650 om, similar to
CATHODOLUMINESCENCE MICROSCOPY AND SPECTROSCOPY OF SHOCKED ZIRCON FROM

THE VREDEFORT IMAPCT STRUCTURE, SOUTH AFRICA. A. Gucsik ' , 'Max Planck Institute for
Chemistry, Dept. of Geochemistry, Joh.-J.-Becherweg 27, D-55l28, Mainz, Germany (E-mail: gucsik@mpch-
mainz.mpg.de)
Introduction: Zircon is a highly refractory and spectroscopical analysis. Compared to CL properties of

weathering-resistant mineral that has proven useful as Ries samples. zircon grains from the Vredefort crater
an indicator of shock metamorphism in the study of exhibit similar CL spectral features as follows. Narrow
impact structures and formations (e.g., [1-6]). Zircon emission peaks centered at 314, 406, 475-484, 580,
has advantages compared to quartz or other shock- and 628 nm with relatively high peak intensities are
metamorphosed rock-forming minerals that have been superimposed on a broad band. The doublet peak at
widely used as impact indicators, but are far less 475-484 dominates CL spectra of all samples (Fig. 2).
refractory than zircon. The purpose of this
investigation is to further investigate the capability of
the SEM-CL technique to document shock
defonnation and to determine whether specific CL a)
effects in zircon can be utilized to detennine particular
shock pressure stages.
Samples and Experimental Procedure: The

Vredefort (South Africa) samples were first examined
under a petrographic microscope. Digital optical
images were stored without further computer
enhancement. The samples were then examined with
an Oxford Mono-CL system attached to a JEOL JSM
6400 scanning electron microscope (SEM). Operating
conditions for all SEM-CL investigations (at Natural
History Museum of Vienna, Austria) were 15 kV
accelerating voltage and 1.2 nA beam current;
backscattered-electron (BSE) and
cathodoluminescence (CL) images were obtained. The
BSE and CL images were captured digitally. CL
spectra were recorded in the wavelength range of 200-
800 nm, with I nm resolution. The grating of the
monochromator was 1200 lines/mm. b)
Results
Backscat/ered-electron (ESE) and
cathodoluminescence (CL) image observations: Planar
Fractures (PFs) associated with the irregular fracture
system are observable in an optical micrograph, BSE
(Fig. la) and CL images (Fig. Ib) of zircon grains
from the Vredefort impact structures (South Africa). In
general, a high density of micro-lamellar feature
system occurred in two orientations can be discernible
in BSE and CL images showing dark lines (Figs. 1a
and b). The widths of individual microstructures vary
from 3 to 10 ~m. This observation indicates the
presence of Planar Deformation Features (PDFs)
corresponding to relatively high shock pressure in
between 20-30 GPa [6]. Some of the grains show an
inverse relationship between BSE and CL brightness. Figure 1. BSE (a) and CL (b) images ofPlanar Deformation
Features (PDFs).
Cathodoluminescence spectrometry: Five Vredefort
zircon samples were selected for the CL
.‫סס‬oo from the lattice by outer shell electrons. Broad intrinsic

emission generally results from self-trapped excitons
"000 (STE), which are highly localised excitons trapped by
.~ their own self-induced lattice distortion. Self-trapped
40000
0 excitons are generally produced in crystals with a
•
] ,.000
deformable lanice (e.g., SiD,), which are characterised
.=•«> by strong electron-phonon coupling.
. '0000
The emission energy of the STE is usually much
lower than the band gap of the material due to energy
'" >0000 lost by phonon emission during the electronic
transition. In the present study, CL luminescence
0 centers are dominated by Dy'· indicated by the
'00 .00 '00 .00 700 800
relatively strongest peaks at 478-491 and 573-586 nm
Wavelength (nm) in the visible light range. According to Blanc et al. [8],
Figure 2. Cathodoluminescence spectra of the shocked a weak emission line at around 630 nm might be
Jlredejort zircon samples.
assigned to Gd h The weak bands at 406 and 548 nm
might be related to Th'· [8].
Discussion: The inverse relationship between BSE and Summary and Conclusions: For all shocked
CL brightness might be explained as follows. samples from Vredefort impact crater, an inverse
According to Remand et al. [7], backscanered relationship between the brightness of the
electrons (BSE) are primary beam electrons that leave backscanered electron (BSE) signal and the
the specimen as a result of a single large-angle corresponding cathodoluminescence intensity of the
scattering event or multiple small angle scattering zonation patterns was observed. The CL spectra of
processes. The fraction of primary beam electrons, unshocked and experimentally shock-deformed
which leave the specimen, TJ = lesEl'lB. increases with specimens and naturally shock-metamorphosed zircon
the mean atomic number of the specimen, where Is is samples are characterized by narrow emission lines
the beam current entering the sample and lesE is the and broad bands in the region of visible light and in the
BSE current leaving the specimen. This dependence of near-ultraviolet range. The emission lines result from
backscattered-electron yield on mean atomic number rare earth element activators and the broad bands
allows for the compositional imaging of flat surfaces might be associated with lanice defects.
with submicrometer resolution, which provides bener Consequeotly, the combination of BSE and CL
spatial resolution and microcompositional infonnation imaging and CL spectroscopy is a potentially useful
than standard optical methods. tool that can be used to characterize the shock stage of
The BSE contrast is sensitive to changes of average zircons from impactites. Our results also give new
atomic number, i.e., higher Z causes bright BSE yield insight into the structural changes that occur in zircons
and lower Z leads to the dark BSE brightness. In the during shock metamorphism, and the pressures
case of natural zircon, the inverse relationship between associated with these changes.
BSE and CL brightness might be caused by high
concentrations of Hf, Y, Yb, V, and Th, corresponding References
[1] Bohor B.F. et aL 1993. Earth and Planetary Science
to high BSE intensities. The CL images of naturally
leiters 119: 419-424. [2) Kama S.L. el al. 1996. Earth and
shock-deformed zircon crystals from the Ries and Planetary Science Le//ers 144: 369-387. [3] Krogh T.E. et a!.
Vredefort impact structures also exhibit an inverse 1996. In: Hart S. and Basu A. (eds.) American Geophysical
relationship between BSE and CL brightness, which Union, Geophysical Monograph 95, pp 343-353. [4] French
indicates that the spatial distribution or abundance of B.M. 1998. Traces of catastrophe: A handbook of sbock-
the above-mentioned elements causes low (dark CL) metamorphic effects in terrestrial meteorite impact
and high (bright CL) intensities. structures. LPI Contribution 954, Lunar and Planetary
The luminescence properties are mostly the result of Institute, Houston, 120 pp. [5] Reimold W.U. et al. 2002.
luminescence-activating ions, such as transition metals, European Journal of Mineralogy 14: 859-868. [6] Wittmann
rare-earth elements, or actinides. According to A. et al. 2006.
Meteoritics & Planetary Science, 41 (3):433-454. [7] Remond
Remond et al. (7] the trivalent rare-earth element G. el al. 2000. In: Pagel M., Barbin Y., Blanc P. and
(REE) radiative recombination centers are Ohnenstetter D. (eds.) Cathodoluminescence in Geosciences,
characterized by sharp visible and near-infrared (NlR) Springer-Yerlag, Heidelberg, pp 59-126. [8J Blanc P. et .1.
emission peaks in the spectrum. The luminescence 2000. In: Pagel M, Barbin Y, Blanc P, Obnenstener D (eds)
results from electronic transitions between the partially Cathodoluminescence in Geosciences, Springer-Verlag
filled 4f shells, which are well shielded (screened) Heidelberg, pp 127-160.
SCANNING ELECfRON MICROSCOPE-CATHODOLUMINESCENCE AND MICRO-RAMAN

PROPERTIES OF KABA CV3 CHONDRITE. A. Gucsik', Sz. Berczi', T. Okumura', H. Nishido', K. Ninagawa',
Sz. Nagy', 'Max Planck Institute for Chemistry, Dept. of Geochemistry, Joh.-J.-Becherweg 27, D-55I28, Mainz,
Germany (E-mail: gucsik@mpch-mainz.mpg.de); 'Eolvos University, Institute of Physics, Dept. Materials Physics,
Cosmic Materials Space R. Group, H- 11 17 Budapest, Hungary; 'Research Institute of Natural Sciences, Okayama
University of Science, 1-1 Ridai-cho, Okayama, 700-0005, Japan; 'Department of Applied Physics, Okayama
University of Science, 1-1 Ridai-cho, Okayama, 700-0005, Japan;
Introduction: Previous petrologic studies [1,2]

suggest that Kaba (kept in Reform College of 16000
Debrecen, Hungary) is the most primitive unshocked
-",..,
CV fall. It is therefore of great interest to us because it
will: (I) give us a better understanding of the effects of
14000
12000
.......
-- ",
-Are. 4
~
parent body processing on the mineralogy of CVs and
10000
allow comparison of these effects with other meteorite
groups, (2) help in determining mineralogy of ~
c
8000
Interplanetary Dust Particles. .!! 8000
.E
Early classification alternately changed from the -'
U 4000
original Wiik type III (1956) [3], to Wood type ll,
(1967) [4], to Van Schmus-Wood C2, (1967) [5], to 2000
Van Schmus and Hayes type C(V)3 (1974) [6], and 0
finally to CV3 oxidized and Bali-type (Krot et aI., 300 400 500 600 700 600
1998) [7]. Its characteristics is also the presence of two Wavelength (nm)
endtype olivines: forsterite (Mg,SiO,) and fayalite
(Fe'+,SiO,), too. Figure 1. CL spectra of four area containing a
In this study, we discuss potentials of use of dominant broad band centered at around 630 nm.
cathodoluminescence and micro·Raman techniques to SEM-CL spectral analyses (at Okayama University oj
study of Kaba meteorite focusing on applications to Science, Okayama, Japan) were performed using a
study of the Interplanetary Dust Particles (!DPs) and Scanning Electron Microscope (SEM), JEOL 5410LV,
macromolecular meteoritic organic material. equipped with a CL detector, OxJord Mono CL2, which
Application to lOPs: It is believed that !DPs were comprises an integral 1200 grooves/mm grating
derived from comets and asteroids. However, to date monochromator attached to reflecting light guide with
the fonnation mechanism of the IDPs is poorly a retractable paraboloidal mirror. The operating
understood. Studies of IDPs provide understandings conditions for measuring BSE (backscattered electron)
about grain dynamics in the early Solar System and images, CL images, and CL spectra were accelerating
presolar interstellar and circumstetlar environments, voltage: 15 kV, and 2.0 nA at room and liquid nitrogen
grain condensation, chemical and physical evolution, temperature (dataji'om Berczi et al. [9]).
and grain density distribution in the proto· planetary
disk. Gucsik et al. [8] suggested cathodoluminescence Their [9] CL spectral and imaging features are in a
would be a means of quickly surveying Stardust good agreement with previous studies. The peak at 630
particles to get a fIrst order indication of their om is assigned as Mn 2+-activator element-related band,
mineralogy and petrology. In their CL study, they used and the shoulder peak at 720 nm might be related to
Semarkona chondrules for the implications for studies Cr'+ [10,1 I]. These activator elements can cause
of !DPs. According to Berczi et al. [9] in the CL relatively high CL intensity parts (CL-bright areas) in
images of fayalite from Kaba shows CL-dark the CL images of forsterite. On the other hand, there is
characters and forsterite exhibits CL-bright area in the a relatively high Fe-content as a major quencher
otherwise CL-dark environment. CL spectra of the element of fayalite, which can produce CL-dark parts
Kaba fine grained samples (powdered) are of the sample. A further micro-Raman spectroscopical
characterized by a dominant broad band, which is characterization will be carried out on these samples to
centered at around 630 nm. An additional shoulder yield more data on the crystallinity of forsterite and
peak is centered at around 720 nm (Fig. I). fayalite.
Implication for study of macromolecular Acknowledgements: This study was supported by

organic material in chondrites: The following HAS-1SPS 10412007 loint Program. Authors are
chapter has been based on the personal communication thankful for Dr. Mihaly Nagy (Reform College of
with Conel M. O'D. Alexander at Carnegie Institution Debrecen) supplying Kaba meteorite specimens for the
of Washington (2004, 2006). The macromolecular further analyses.
organic material is the most abundant organic material
in chondrites, but remains poorly understood. It is References: [1] Krot et al. (1998) Meteoritics Planet.
thought to be largely interstellar in origin [12]. Sci. 33. 1065-1085. [2] Bonal et al. (2004) LPS ..\:XXV,
However, a solar system origin for some of the #1562. [3] Wiik, H. B. (1956): GCA. 9, 279; [4] Wood, 1. A.
macromolecular material can't be ruled out, and it has (1967): GCA. 31,2095; [5] Van Schmus W. R. & Wood 1.
been modified by processes in the meteorite parent A., (1967) GCA. 31,737; [6] Van Schmus W. R. & Hayes, 1.
bodies and, possibly, in the solar nebula (e.g. M., (1974) GCA. 38, 47; [7] Krot A. N., Petaev M.I., Scott
Alexander et aI., [13]). It may also have been the E.R.D., Keil K. (1998) LPSCXX/X, #1552; [8] Gucsik et al.
source of the soluble organic material in meteorites (2007) LPS ..\:XXVIII. #/05/. [9] Berczi et al. (2008) LPS
that include amino acids and nucleic acids (e.g. Cronin XXX/X. #J657. [10] Benstock E. 1. et al. (1997) Am. Mineral.
et aI., [14]). It has been shown that some optically 82, 310-315. [1 t] Steele I. M. (1986) Am. Min., 7t, 966-970.
active soluble compounds, including amino acids, have [12] Yang and Epstein (1984) Nature 31 I, 544-547. [13]
slight L-enantiomer excesses [15,16]. Meteorites and Alexander et aL (1998) Meteoritics Planet. Sci. 33, 603·622.
interplanetary dust (IDPs) would have been a [14] Cronin et al. (1988) In: Meteorites and the early solar
significant source of complex organic material on early system, pp. 819-857. [15] Cronin and Pizzarello (1997)
Earth. Given the L-enantiomer excesses in meteorites Science 75, 951-955. [16] Pizzarello and Cronin (2000)
and in all living organisms, it has been suggested that Geochim. Cosmochim. Acta 64, 329·339. [17] Huss et aL
extraterrestrial organic matter may have played a role (2003) Geochim. Cosmochim. Acta 67, 4823-4848.
in the origin of life.
Thus, the organic matter in meteorites potentially
retains a record of processes that occurred in the
interstellar medium, in the solar nebula and in
meteorite parent bodies. Unraveling this history is of
considerable interest to astronomers and meteoriticists.
Since it would have been a significant source of
complex organic material on the early Earth,
understanding what the products of its weathering were
under early Earth conditions is also an important goal
for Astrobiology.
Based on noble gas abundances in presolar
components, Huss et al. [17] suggest that the volatile
element fractionations are the result of modest heating
in the nebula prior to chondrule formation and
chondrite accretion. This heating would have
significantly modified the organic material. They based
their conclusions in part on data from the CVs
Vigarano and Leoville. If, as expected, we find that the
organic matter in Kaba is more primitive than in
Vigarano and Leoville, this will show that they have
underestimated the role of parent body processing in
modifying the noble gas abundances, and would go
some way to disproving their model. After the organic
analyses, we will also attempt to measure presolar
noble gas abundances in the Kaba residue to further
test their model. A multiple technological approach of
cathodoluminescence and micro-Raman spectroscopy
can aid to understand more about these models.
CATHODOLUMINESCENCE CHARACTERIZATION OF NANODIAMO 'OS: A ' APPLICATION TO

THE METEORITIC NANODIAMONDS. A. Gucsik', H. Nishido' and T. akazato', K. Ninagawa', 'Max Planck
Institute for Chemistry, P. O. Box 3060, D-55020 Mainz, Germany, (E-mail: gucsik@mpch-mainz.mpg.de);
'Research Institute of Natural Sciences, Okayama University of Science, I-I Ridai-cho, Okayama 700-0005, Japan;
'Department of Applied Physics, Okayama University of Science, I-I Ridai-cho, Okayama 700-0005, Japan.
Introduction: Primitive meteorites contain abundant diamonds but very rare (about 0.1 %) among natural
(up to 1500 ppm) amounts of nanodiamonds. At least diamonds - contain nitrogen as isolated single nitrogen
some subpopulation must be of pre-solar (stardust?) atoms called "C Centers". Sometimes type I diamonds
origin, as indicated by the isotopic composition of may also contain clusters of three nitrogen atoms
trace elements the diamonds carry, in particular noble called "N3 Centers".
gases [I) and tellurium [2]. On the other hand, the
isotopic composition of the major element, carbon, is
unremarkable, Le. within the range reasonably
,.., .-
uwn·lU
-Diamond/AI
- DiamondJA2
- DiamondlBl
-DiamondlB2
expected for Solar System materials [3]. Two main - DiamondfC I
theories exist for the fonnation process of the -Diamond1C2
meteoritic nanodiarnonds (e.g.,[4]·and references - DiamondI'Dl
- DiamondlD2
therein): (I) qemical vapor deposition (CVD), and
(2) shock origin. TEM investigations, in particular,
seem to suggest that fonnation by a CVD process is
most likely [4].
Samples and Analytical Procedures: K2 W....lerIgthIMl)
(Ultradispersed Detonation Diamonds-UDD)
Figure 1. Cathodoluminescence spectra of K2 nandiamond
nanodiamonds were mounted in the non-radiative
_.
samples: Intensity vs wavelength.
epoxy material. Their size dimensions were grouped
,,",.-------------------,
into the following groups: less than 3nm (Diamond:
NI and A/2), between 3-7 nm (Diamond: BII and ),OI,l.IO.:l.,.
B/2), bigger than 7 nm (Diamond: C/I and C/2), and a
I
n"
mixture (Diamond: DII and D/2) all of them. CL
measurements were obtained on carbon-coated,
polished (by silicon colloids) thin sections. Color CL
imaging was performed on a CL microscope. The
system was commonly operated at 15 kV accelerating
voltage and a beam current of 0.5 rnA. CL colour
images were captured using a digital
photomicrographic camera system. High-resolution CL
-
images and spectra were acquired using a scanning
electron microscope (SEM at Okayama University of "
Figure 2. Cathodoluminescence spectra of K2 nandiamond
Science, Okayama, Japan) equipped with an grating- samples: Intensity \IS eV.
type monochromator, SEM-CL system. This system
was operated at 15 kV accelerating voltage and a probe Consequently, the examples of exotic applications
current of 1.5 nA. CL spectra were recorded in the (astrochemica!) ofUDD as analog of interstellar grains
wavelength range of 350-800 nm with I nm spectral in laboratory simulation experiments would be
resolution and a dwell time of I second per step by demonstrated by the cathodoluminescene techniques.
photon counting. Further comparative studies will be done using
Results and Discussion: Cathodoluminescence
meteoritic nanodiamonds samples (e.g., yielded from
spectral features of all K2 samples show two broad
Allende meteorite).
bands centered at around 388 (3.1 eV; A-center) and
452 (2.69 eV; -center) nm (Figs. I and 2). According References: [I} Hu<>s, G.R, & Lewis, R.S. Meteoritics, Vol. 29,
to Pratesi [5] in an agglomerated state: such 1994, P 791; [2} Richter, S.,on. U., & Begemann, F. Nature, Vol
agglomerates are called "A Centers" when occur as 391, 1998, p 261; [3} Russel. 8.S., Arden, lW., & Pill inger, C.T.
Science, Vol 254, p 1188;[4] Daulton, T.L., Eisenhour, D.O.,
pairs of nitrogen atoms (type laA), "B centers" when Bematowitz., T.J., Lewis, R.S., & Buseck, P.R. Geochimica et
occur as four nitrogen atoms surrounding a common Cosmochimica Acta, Vol. 60, 1996, p 4853; {5] Pratesi, G., 2009. In:
vacancy (type laB) and mixtures of them may also A. Gucsik (cd) Cathodoluminescence and its application in the
occur. Type Ib - mostly represented in synthetic Planetary Sciences, Springe, pp. 160.
Thermo-luminescence glow curves and photoluminescence of ion irradiated Ah03

K.S.Jheeta
S. M. S. Medical College, J L N Marg, Jaipur -302004, India
kuldeep. jheeta@gmail.com
Introduction: Thermo-luminescence (TL) spectra Figures:

of single crystals of Al,03 (sapphire) irradiated
with 200 MeV swift Ag ions at different fluence =
in the range IxlO II to Ixl0 13 ions/em' has been ~
(I) 1xl0"
(ij) 5x10"
recorded at room temperature by keeping the (d) 1xl0"
=
warming rate 2K1min. The TL glow curve of the
irradiated samples has a simple structure with a
ie =
(e)
(b)
(a)
5xl0"
1xl0"
prtstine
prominent peak at - 500 K with one small peak at "~ "'000

650 K. The intensity of main peak increases with ~
the ion fluence. This has been attributed to the
",'"'"
~
creation of new traps on irradiation. Also, a shift
of 8 K in the peak position towards low tempera-
ture side has been observed at higher fluence Temperature (K)
I X10 13 ions/em'. In addition, photoluminescence

(PL) spectra of irradiated samples have been rec- Fig.I. Thermo-luminescence glow curves for pristine and
orded at room temperature upon 2.8 eV excita- sapphires irradiated with 200 MeV Ag ions at various flu-
tion. A broad band consisting of mainly two ence.(fluence in ions/cm 2).
emission bands, respectively at 2.5 and 2.3 eV
corresponding to F, and F,2+ defect centers is ob- "00 (I) 1x10"
served. The intensity of these bands shows an in- (e) 5x10"
creasing trend up to fluence 5XlO I' ions/em' and

"00 (d) 1x10"
(c)Sx10"
then decreases at higher fluence I XlO I3 ions/em'. ~, '000 (tI) 1x10"

(a) prtstine
The results are interpreted in terms of creation of f! .00
newly defect centers, clustering/aggregation and "

~
~
.00
radiation-induced annihilation of defects. ~ '00
Keywords: Sapphire; Thermo-luminescence; Pho-

toluminescence; Defect centers. ,. ,.
" '.0
Energy (eV)
PACS codes: 78.66.Nk; 78.60.Kn, 78.55.-m,

61.72.-JI. Fig.2. Photoluminescence spectra of pristine and sapphires
irradiated with different fluence of Ag ion. (fluence in
ions/cm 2)
46 LPI Contribution No.1 473
References:
1. K. Nassau, The Physics and Chemistry of

Colors, Wiley Interscience, 1983.
2. K.S. Jheeta, D.C. Jain, R. Kumar, F. Singh,
K.B. Garg, J. Nucl. Mater. 353 (2006) 190.
3. B.D. Evans, 1. Nucl. Mater. 219 (1995) 202.
4. B.D. Evans, G.J. Pogatshnik, Y. Chen, Nucl.
Instr. Meth. B 91 (1994) 258.
5. Y. S. Horowitz, Thermoluminescence and
Thermoluminescent Dosimetry, Vol. I, CRC
Press, Inc. 1984.
6. C. Jardin, B. Cannut, S.M.M. Ramos, J. Phys.
0: Appl. Phys. 29 (1996) 2066.
7. E.R. Hodgson, Defects in insulating Materials,
Ed. Kaner! and Spaeth, World Scientific,
1993.
8. A. AI Ghamdi, P.D. Townsend, ucl. Instr.
Meth. B 46 (1990) 133.
9. T. Tanabe, M. Fujiwara, K. Miyazaki, J. Nucl.
Mater. 233-237 (1996) 1344.
10. B. Henderson, G.F. Imbusch, Optical
Spectroscopy of Inorganic Solids, Oxford
Science Pub. 1989.
MICRO-RAMAN SPECTROSCOPY OF DIAMONDS FROM JaH 054 AND SAHARA 98505

UREILITES, STATISTIC RESEARCH. A. Karczemska I, T. Jakubowski', M. Kozanecki 3, M. Szurgot', A.
Gucsik 5, S. Mitura 2. I Technical University of Lodz, Institute of Turbomachinery, Wolczanska 219/223, Lodz,
Poland (anna.karczemska@p.lodz.pl); , Technical University of Lodz, Institute of Materials Science and
Engineering, Stefanowskiego 1/15, Lodz, Poland; 3 Department of Molecular Physics. Technical University of
Lcdz, Poland; 4 Technical University of Lodz, Center of Mathematics and Physics, Politechniki 11, Lodz Poland;'
Max Planck Institute for Chemistry, Department of Geochemistry, Mainz, Gennany, Joh.-J.-Becherweg 27, D-
55128;
Introduction: Ureilites are ultramafic, coarse The results indicate that diamonds Raman shifts were
grained primitive achondrites. They are mainly between 1322,81 cm· 1 and 1334,03 em-I in JaH 054,
composed of olivine and pigeonite [1]. They are also and from 1329,13 em-I to 1334,58 em· 1 in Sahara
known to contain carbon, represented by graphite, 98505 (Fig. 2). A wide spread ofFWHM (full width at
diamond, amorphous carbon and carbide. Other half maximum) parameters were also seen, from 0,75
accessory phases are iron and sulfide. When present, em -I to 13,37 em-I in JaH 054, and 5,02 em-I to 37,65
the carbon usually fills the spaces between olivine and em-I in Sahara 98505 (Fig. 3).
pyroxene minerals, but it also sometimes occurs inside
them. Diamonds are usually I - I0 ~ size. The origin • JaH054 • Sahara 98505
of diamonds in this enigmatic group is well discussed
by various authors, and has been explained in various
ways including the theory of metamorphic ,."
0"
transfonnation of graphite during impact, as well as the c
theory that they fonned through a process of chemical ,• •
.. .
0"
vapor deposition (CVD) in the solar nebula [2-6J. •"
Experiments: We examined polished slices of two
ureilites: JaH 054 and Sahara 98505. The choice of
these ureilites was based on preliminary investigations
o •
•
1323 1324 1325 132e 1327 1328 1329 \330 1331 1332 1333 1334 1335
Raman shIft [cm-1]
which shown that they posses relatively high diamond
content [3]. The samples used were fe-polished with
Figure 2. Distribution of the diamond Raman peak
non-diamond powder.
position in JaH 054 and in Sahara 98505 ureilites.
Record of Raman spectra was done on a confocal
Raman micro-spectrometer T-64000 (Jobin-Yvon)
JaH 054 shows a relatively narrow FWHM range of
equipped with the BX-40 microscope (Olympus). The
diamond peaks in comparison to Sahara 98505 (the
514.5 nm Ar line was used for sample excitation.
mean value of FWHM for JaH 054 is 6,53 em-I and
Acquisition time and laser power were adjusted to
mean value ofFWHM for Sahara 98505 is 18,12 em-I).
obtain spectra of sufficient quality. The laser beam
diameter was 1.5 ~m, and the light intensity across the
beam was of Gaussian distribution. • JaH 054 • Sahara 98505
Results: Our analysis is based on 43 different "

diamond Raman peaks from JaH 054 and on 27 peaks ,.
from Sahara 98505. Typical diamond and graphite u
C •
peaks for both ureilites are shown on Figure 1. ,•
0' •
•
o I I I I I I
I 3 5 1 9 II I' 15 11 W ~ ~ ~ v ~ ~ u ~ D
FWHM [cm-l]
Figure 3. Distribution of the diamond Raman peak
,- .- FWHM of JaH 054 and Sahara 98505 ureilites.
Figure 1. Examples of Raman spectra of Sahara 98505

and JaH 054.
• JaH 054 ... Sahara 98505

References: [I] Clayton R. N., Mayeda T. K.
• (1988) Geochim. Cosmochim. Acta, 52, 1313. [2]
Miyamoto M. Matsuda J. Keisuke I. (1988) Geophys.l
. .. • Res.Lett., 15, 1445. [3] Jakubowski T. Karczemska A.
%
~15
~1O
"
o
• •
.. ~
•••
•
• • •
••
•
.'~. ~.
~
~
Kozanecki M. Gucsik A. Stanishevsky A. Mitura S.
(2009) 40th LPSC Abstract #1382. [4] Miyamoto M.
Takase T. Mitsuda Y. (1993) Mineral., 16, 246-257.
[5] Miyamoto M. (1998) Antarct. Meteorite Res.,
11,171 - 177. [6] Karczemska A. Szurgot M. Koza-
1322 1324 1326 1328 1330
Raman shift (cm-1)
1332
"'. 1336 necki M. Szynkowska M. I. Ralchenko V. Danilenko
V. V. Louda P. Mitura S. (2008) Diamond & ReI.. Mo-
Figure 4. Plot of the diamond Raman peak position ter., 1.7, 1179-1185.
versus FWHM of JaH 054 and Sahara 98505 ureilites
The FWHM of the diamond peak against the

Raman shift of diamond band shows some degree of
correlation (Fig. 4). The mean values of diamond
Raman shifts for both samples are similar, 1331,64 em'
, for JaH 054 and 1332,1 cm- l for Sahara 98505.
Conclusions: Our research of two ureilites JaH
054 and Sahara 98505, based on micro-Raman
spectroscopy, proves the occurrence of different kinds
of diamonds in both samples.
Various Raman shifts show the significant diamonds
differences occurring both, inside one and the same
sample and among the samples. The Raman peak
positions in some cases are shifted towards smaller
wavenumbers, this could indicate the presence of
lonsdaleite. Interesting is that some peaks are shifted
toward higher wavenumbers: 1334 em'), even to 1335
em·' for Sahara 98505.
The diamond peaks most often coexist with
graphite phases, but sometimes only diamond peaks are
observed. This could be explained by the bigger size of
diamonds in comparison to the area being sampled by
the laser, or the graphite phase simply does not exist
around these diamonds.
In few cases the diamond peak is broad and
consits of two merged maxima. The different groups
ofdiamonds (potentially different polytypes) sometimes
coexist together. FWHM of diamonds synthesized by
CVD process range from 3 cm· l to 25 cm- l [2-4]. The
FWHM values of JaH 054 diamonds are similar to
FWHM of CVD diamonds and differ significantly in
comparison to shock-produced diamonds, what agrees
well with the results by Miyamoto and coworkers [2-4].
However, FWHM of diamond Raman peaks of Sahara
98505 ranges from 5,02 em·' to 37,65 cm- l which is
much broader range than that exhibited in ureilites
studied by Miyamoto group.
We hope that ureilitic diamonds will help in
understanding of the origin of. extraterrestrial
diamonds.
CATHODOLUMINESCENCE AND RAMAN SPECTROSCOPIC CHARACTERIZATION OF

EXPERIMENTALLY SHOCKED PLAGIOCLASE. M. Kayama', A. Gucsik', H. Nishida', K. Ninagawa' and,
A. Tsuchiyama4 IResearch Institute of Natural Sciences, Okayama University of Science, 1-1 Ridai-cho, Okayama,
700-005, Japan (kayamaOI27@gmaiJ.com), 'Department of Applied Physics, Okayama University of Science I-I
Ridai-cho, Okayama, 700-0005, Japan, 'Max Planck Institute for Chemistry, Department of Geochemistry, Joh.-J.
Becherweg 27, D-55128 Mainz, Germany, 4Department of Earth and Space Science, Osaka University, 1-1 Machi-
kaneyama, Toyonaka, Osaka 560-0043, Japan.
Introduction: Cathodoluminescence (CL) spec- much maskelynite. It indicates that CL spectral peak at
troscopy and microscopy provide useful information 420 nm is characterised by the existence of maskely-
on existence and distribution of defect and trace ele- nite. Raman spectrum of unshocked plagioclase shows
ments in minerals. CL intensity and peak position de- a pronounced peaks at around 170, 280, 480 and 510
pend mainly on activator concentration, composition cm- 1, whereas the spectra of shocked plagioclase at 20
and crystal fields, which might be related to genetic and 30 GPa exhibit two peaks at around 480 and 510
conditions of the formation and subsequent metamor- cm- I . Their Raman intensities also decrease with an
phism such as shock events. Futhermore, CL features increase in shock pressure. Shocked plagioclase at 40
are affected by shock pressure including a post-shock GPa shows a weak and broad spectral peak at around
temperature effects. This fact indicates that CL might 450 cm-!, which can be assigned to T-O-T symmetrical
be a useful technique to evaluate the stage of shock stretching vibration. These results suggest that peak
metamorphism in the rock-forming minerals such as shift of CL spectral peak at around 470 nm might be
plagioclase. In this study, CL and Raman measure- caused by the alteration of crystal field related to Mn2+
ments of experimentally shocked plagioclase activator. Raman spectral analysis indicates that higher
(AbooA14o) at 0, 20, 30 and 40 GPa were carried out shocked plagioclase at 20 and 30 GPa have their lower
for the evaluation of shock metamorphic effect on crystallinity without any change of framework confi-
them. guration. It is responsible for a decrease in CL intensi-
Sample and methods: Polished thin sections of ty with an increase in shock pressure. These results
unshocked and experimentally shocked plagioclase imply that CL and Raman spectroscopy of plagioclase
(AbooAl4o) at 20, 30 and 40 GPa were employed for can be expected to evaluate shock pressure induced in
CL and Raman measurements. CL spectra were car- terrestrial and meteoritic samples.
ried on in the range from 300 to 800 nm using a secan- References
dary electron microscope-cathodoluminescence (SEM- [1] Mariano et a1. (1973) Geol. Soc. Amer., Abstract #5,
CL) system, which is comprised of an SEM (JEOL: 726 [2] Marfunin, A. S. (1979) Springer-Verlag, Ber-
J8M-5410) combined with a grating monochromator Iin,352
(OXFORD: Mono CL2). The Raman spectroscopy
was perfonned using a Raman micros-spectrometer
~
(JASCO: NRS-2100) with an Ar laser of 514.5 nm
- 2 0 GPo
wavelength. -"'GPo
Results and discussion: CL spectra of unshocked -40GPo
plagioclase have four broad peaks at around 350, 420,
570, and 750 om, which can be assigned to Eu2+, struc-
tural defect, Mn 2+, and Fe3+ center, respectively (Fig.
1)[1,2]. Their CL intensities decrease with an increase
in experimentally shock pressure, whereas CL spectral
peaks assigned to Mn2+ only appear in shocked pla-
gioclase at 30 GPa. The wavelength of this spectral
peak shifts from 570 nm for unshocked plagioclase to
630 nm for shocked plagioclase at 20 and 30 GPa. CL
spectral peak at 420 om is observed in plagioclase
Fig. I CL spectra of unshocked and experimentally
shocked at 40 GPa, whereas it has not been recognized
shocked plagioclase at 20, 30 and 40 GPa.
in the plagioclase at 0, 20 and 30 GPa. This peak
might be assigned to self-trapped exciton (STE). Simi-
lar blue emission has been observed in maskelynite
from Dhofar 019 and Shergotty, which consist of
CATHODOLUMINESCENCE CHARACTERIZATION OF MASKELYNITE AND ALKALI FELDSPAR

IN SHERGOTTITE. M, Kayamal, T. Nakazatol, H, Nishida), K. Ninagawa2 and A. Gucsik 3 lResearch Institute of
Natural Sciences, Okayama University of Science 1-1 Ridai-cho, Okayama, 700-0005, Japan (kaya-
maOI27@gmail.com), 'Department of Applied Physics, Okayama University of Science I-I Ridai-cho, Okayama,
700-005, Japan, 'Max Planck Institute for Chemistry, Department of Geochemistry, Joh.-J. Becherweg 27, D-55128
Mainz, Germany.
Introduction: Martian meteorite of shergottite is broad band peaks at around 400 (defect center) and
regarded as one of the meteorites induced by highest 750 nm (Fe 3+ impurity center).
shocked pressure, which causes phase transfonnation Both ofmaskelynite in Dhofar 019 and Shergottite
of plagioclase into maskelynite. It has been severely show a weak and broad Raman spectral peak at around
shocked and is considered a "type material" for maske- 450 em'l, which is related to T-O-T symmetrical stret-
Iynite. Cathodoluminescence (CL) features such as CL ching vibration, although a terrestrial plagioclase has
intensity and peak position are related to composition, pronounced and narrow Raman spectral peaks at
concentration of luminescence center and crystal fields, around 170,280,480 and 510 cm-'. Raman spectra of
which can be altered by the pressure produced by alkali feldspar in Dhofar 019 and Shergotty also have a
shock metamorphism such as impact events. In this broad peak at 500-600 cm-', whereas terrestrial coun-
study, CL spectroscopy and microscopy of maskely- terpart shows pronounced and narrow Raman peaks at
nite and alkali feldspar in shergottite (Dhofar 019 and 280, 400, 470, 520 and 1120 cm-'. It indicates that
Shergotty) were carried out. These results have been high shock pressure at 40 GPa converts plagioclase
compared to CL data for experimentally shocked pla- into maskelynite accompanied by highly deformed or
gioclase to interpret shock pressure effect on CL prop- partly amorphous state in alkali feldspar. This pheno-
erties of these samples. menon eliminates their luminescence centers, respon~
Sample and Methods: Polished thin sections of sible for weak CL intensities of maskelynite and alkali
shergottite (Dhofar 019 and Shergotty) were selected feldspar in Dhofar 019 and Shergotty compared to
for CL and Raman measurements. Shergotty exhibits terrestrial samples and disappearance of a broad band
of dull gray-green pyroxene prisms up to 1 em long peak at around 750 nm for alkali feldspar in these
with colorless lath-like and interstitial vitreous maske- meteorites.
Iynite, which replaced the feldspar [1). Dhofar 019 is References:
classified as an olivine-bearing basaltic shergottite [I] http://curator.jsC.nasa.gov/almetlmmclindex.cfm
consists of subhedral grain (0.2-0.5 mm) of pyroxene [2) Badjukov D. D et al. (2001) LPS XXXII, Abstract
(pigeonite and augite), olivine and feldspar mostly #2195. [3) Taylor L. A et aI. (2002) Meteoritics &
converted to maskelynite and minor alkali feldspar, Planetary Science, 37, 1107-1128.
merrillite, chromite, ilmenite and pyrrhotite, associated
with terrestrial secondary phases. Shock pressures of
these shergottites were qualitatively estimated in the
range of30-35 GPa for Dhofar 019 and above 40 GPa
for Shergotty [1-3].
Results and Discussion: CL spectra of maskely-
nite in Dhofar 019 and Shergottite exhibit two broad
band peaks at around 400 and 600 nm, which can be
assigned to self-trapped exciton (STE) and Mn'+ im-
purity center, respectively. Similar blue emission at
around 400 nm is observed in only plagioclase expe-
rimentally shocked at 40 GPa. It implies that a broad
band peak at around 400 nm is characteristic of maske- o ........._._..;.J.. .. -l.. ~ .• J.... _ _
Iynite. Futhennore, a broad band at around 600 nm in :m 400 !500 1500 700 800
W_(rm)
maskelynite shows rather weak intensity compared to
terrestrial plagioclase.
Fig. 1 CL spectra of unshocked and experimentally
CL spectra of alkali feldspar in Dhofar 019 and
shocked plagioclase at 20, 30 and 40 GPa and maske-
Shergottite have a broad band peak at around 400 nm,
Iynite in Dbofar 019.
whereas terrestrial alkali feldspar actually consists of
CATHODOLUMINESCENCE OF SHOCKED PLAGIOCLASE AND ALKALI FELDSPAR FROM RIES

CRATER, GERMANY. M. Kayamal, H. Nishido!, K. Ninagawa2 and A. Gucsik 3 IResearch Institute of Natural
Sciences, Okayama University of Science 1-1 Ridai-cho, Okayama, 700-005, Japan (kayamaOI27@gmail.com),
'Department of Applied Physics, Okayama University of Science I-I Ridai-cho, Okayama, 700-0005, Japan, 'Max
Planck Institute for Chemistry, Department of Geochemistry, Joh.-J. Becherweg 27, 0-55128 Mainz, Germany.
Introduction: Cathodoluminescence (CL) micro-

scopy for quartz and feldspar minerals in suevite from
Ries Crater, Germany has been used for interpretation
of shock pressure effects .. CL spectroscopy for these
minerals, however, has not been investigated in detail.
In this study, CL spectroscopy combined with CL mi-
croscopy was carried out to investigate shock pressure
effect on plagioclase and alkali feldspar in suevite
from Ries Crater, Gennany.
Sample and methods: Alkali feldspar (Or,oA!>'o)
and plagioclase (Ab"A.n,,) with PDFs (Planar defor-
mation features) in suevite from Ries Crater were se-
lected as polished thin sections for the optical micro-
scope investigation. CL image and spectra were ob-
tained using a secondary electron microscope- Fig. 1 CL image of plagioclase in suevite from
cathodoluminescence (SEM-CL) system. Ries Crater, Gennany
Results and Discussion: CL spectra of plagioc-
lase from Ries Crater show three broad peaks at
around 400, 560 and 700 nm, which can be assigned to
defect center and Mn 2+ impurity center and Fe3 + impur-
ity center, respectively. Similar CL peak at around 400
nm is observed in experimentally shocked plagioclase
at 40 GPa and maskelynite in shergottites. Broad peaks
at around 400, 560 and 700 nm in this plagioclase ex-
hibit rather weak intensities compared to unshocked
terrestrial plagioclase.
Alkali feldspar from Ries Crater has a broad CL
peak at around 400 run assigned to defect center. In
general, unshocked terrestrial plagioclase consists of
two broad spectral peaks at around 400 and 700 nm
(Fe 3+ impurity center). Alkali feldspar in shergottite
also shows only a CL spectral peak at around 400 nm. Fig. 2 CL image of alkali feldspar in suevite from
In the CL image, plagioclase and alkali feldspar Ries Crater, Germany
exhibit heterogeneous distribution of CL intensities as
thin dark lines superimposed on more brightly lumi-
nescence background (Figs. I and 2). These thin dark
lines corresponding to POFs observed under an optical
microscope. It might be caused by impact-shocked
metamorphism. This fact indicates that CL imaging
can be used to detect PDFs in shocked feldspar miner-
als.
52 LPJ Contribution No. J473
CONFOCAL RAMAN IMAGING OF FLUID INCLUSIONS IN GARNET FROM DIAMOND-GRADE

METAMORPHIC ROCKS (KOKCHETAV MASSIF, NORTHERN KAZAKHSTAN). A. V. Korsakov 1 , T.
Dieing2 and A.V. Golovin!, Jan Toporski2 !institute of Geology and Mineralogy of Siberian Branch Russian Acad·
emy of Sciences, Koptyug Pr. 3, Novosibirsk 630090, Russia, korsakov@uiggm.nsc.ru, 'WITec GmbH Ho-
ervelsinger Weg 689081 Vim Genmany, thomas.dieing@witec.de.
Introduction: Study of pre- to syn-peak high pres- accuracy of about 3nm in the lateral and O.3nm in the
sure or ultrahigh-pressure fluids provides an important horizontal direction. During the scans, complete Ra-
insight into subduction processes and recycling of man spectra were acquired at every point and through
some elements between subducted crust and mantle analysis of the spectra, the images shown in Fig. I and
wedge. However, well preserved fluid inclusions are 2 were extracted. Further experimental details can be
exceptionally rare in diamond-grade metamorphic £oun d·m T abl e 1
rocks and generally are too small to be investigated by XY Scan YZ (Denth) Scan
classical techniques of fluid inclusions study, yet they Scan Size 60x50 wn' 50x20 wn'
are suitable for investigation using transmission elec- Resolution I20xlOO 100x50
tron microscopy (TEM; [1-3] and references therein). (pixels)
TEM studies of diamond from the Kokchetav massif Integration 0.162s 0.162s
(Northern Kazakhstan) and Erzgebirge (Genmany) TimelPixel
revealed that they contain fluid and melt inclusions [I, Soectrometer UHTS300 VHTS300
4]. Simultaneously, melt inclusions were found in gar- Grating 600 600
net and clinopyroxene of the same rock types [5], but (lrrooveslmrn1
thus far there is no information available about fluid Objective WOX air WOX air
inclusions in minerals from diamond-grade metamor- rnA 0.91 rnA 0.91
phic rocks. Fluid inclusions are relatively well estab- Excitation 532nm 532nm
lished in coesite-grade metamorphic rocks [6, 7J, how- wavelength
ever, only [8] reports about CO 2 fluids coexisting with Back-Illuminated CCD
CCD Camera
diamond and carbonates in garnet from UHPM Rho- (ontimized for VIS detetion)
dope massif have ben published. Recent findings of
multiphase solid (MS) inclusions in HP or VHPM
minerals were interpreted as "supercritical" fluids [9],
while it is most likely that they represent hydrous sili-
cate melts (see [10, 11] and reference therein for dis-
cussion). In this paper we preset the preliminary re-
sults of fluid inclusions studies from diamond-grade
metamorphic rocks from the Kokchetav massif using
Confocal Raman Imaging.
Geological Settings and Samples: The geological
setting of the Kokchetav massif (Northern Kazakhstan)
has been summarized elsewhere (e.g. [12-18]). The
Kumdy-Kol microdiamonds deposit is dominated by
foliated metapelites, alternating with metacarbonates
and migmatites with lenses of eclogites. The "normal" Fig. 1. XY Raman Image of the inclusion. The Raman
fluid inclusions were found exclusively in diamond- spectra of the garnet show some significant variations
free but diamond-grade calc-silicate rocks, while mul- in the relative peak intensities (Fig. Ic). The spectra
tiphase solid inclusions representing crystallization shown above are normalize to the peak near 900 cm- 1
products of UHP melts were identified in different and the differences are clearly visible between the red
lithologies [5, 20]. Fluid inclusions exclusevely occur and the magenta spectra (especially from the peak near
within the core of garnet porphyroblasts. Confocal 850 cm'] and near 360 cm- I ; here the magenta curve is
Raman Imaging was perfonmed using an alpha300R overlapped by the orange curve). The orange spectra
Confocal Raman Microscope (WITec, Genmany). This shows the calcite. The aqueous phase showed some
instrument combines an ultra-sensitive spectrometer significant differentiation, which can clearly be seen
equipped with a back-illuminated CCD camera with a from the spectra shown on the right (t). Cal~calcite,
high throughput confocal microscope. A piezo-electric H20-Li = Ii uid water, Grt= arnet
scanning stage guaranteed sample positioning with an
on micro-thermometry. Due to the high level of confo- phase inclusions, captured by growing in garnet during
cality, confocal Raman imaging allows non-destructive prograde stage at peak metamorphic conditions. Re-
and noninvasive analysis of such features. cently, these processes were studied experimentaly
The garnet was polished so that the inclusion re- [21]. [2 I] found that these porcesses cause formation
mained intact some tens of microns below the surface. of new garnet with a distinctly different composition
The video image acquired using the alpha300R (Fig compared to the initial host-garnet. (iii) Originally, the
1a,d and 2a,d) show the liquid inclusion. As can be inclusions were traped as melt inclusions. Subsequent
seen in Figs. 1c and 2c , the garnet Raman Spectra crystallization of these melt inclusions liberate some
show significant variation in relative peak intensities fluid phase, which were dissolved in the melt. Newly
across the scanned area. The spectra in Fig. 1c and 2c formed garnet + solid phases (e.g. calcite, chlorite,
are normalized to the peak near 900 ern-I. Differences mica) occur as daughter or xenogenic phases in fluid
are apparent between the red and the magenta spectra inclusions, would then have crystallized from the melt.
(peaks near 850 and 360 ern·'). The orange spectrum It is worth to noted that independently from mecha-
represents a carbonate phase (calcite) in direct prox- nism of origin of these fluid inclusions, newly formed
imity to, or as part of the inclusion. This variation is garnet could appear as result of reaction interaction
confirmed in the depth scan (Fig. 2). Here too, spectra between the inclusions and host-garnet. Similar fea-
are normalized to the peak near 900 cm-\ differences tures were found in run product of high pressure ex-
are apparent between the red and the magenta spectra periments (at T~900-IlOO°C and P~4 GPa) with gar-
(peaks near 850 ern·' and near 360 ern·'; Fig.2c). Inter- net from different metamorphic complexes [21]. The
estingly, the aqueous phase showed significant varia- origin of the texures is then associated with partial
tion, which can clearly be seen from the spectra shown melting of polyphase inclusions in situ [21]. All their
in Figs. If and 2f, both for the X-Y- and the Y-Z-scan. garnets conatin abundant inclusions of hydrous miner-
Based on the analysis of the Raman spectra, only low als and carobates. Breakdown of these minerals at HP
salinity H20-fluids have been recognized. Changes in and HT conditions would liberate some fluids. This
garnet peak intensities appear only around the inclu- fluid could cause partial melting locally and promote
sion. recrystallization of host-garnet. Quenching of the run
products in experiments performed by [21], however,
do not allow us to trace an evolution of the melt pock-
ets during slower cooling and decompression. Crystal-
lization of these melts during retrograde stage may
liberate some fluid, which would most probably be
characterized by low concentration of soluble compo-
nents.
References: [I] Hwang S.-L. et ai. (2005), EPSL, 231,
295- 306. [2] Hwang S.-L. et ai. (2006), EPSL, 243, 94-
Fig. 2. In the YZ (Depth) Scan, the Gamet signal again 106. [3] Dobrzhinetskaya L. F. et al. (2007) PNAS, 104,
shows some significant variations in the relative peak 9128--9132. [4] Dobrzhinetskaya L. F. et al. (2006) EPSL,
intensities. The spectra shown above are normalize to 243,85-93. [5] Korsakov A. V. and Hermann J. (2006),241,
the peak near 900 cm- l and the differences are clearly 104-118. [6] Fu R et al. (2001). JMG, 19,529-545. [7] Fu
visible between the red and the magenta spectra (espe- R et ai. (2003), JMG, 21, 561-578. [8] Perraki M. et ai.
cially from the peak near 850 cm- I and near 360 em-I). (2006) EPSL, 241, 672-685. [9] St6ckhert B. et al. (2001)
It seems as if (also based on the results of the XY scan Geology 29, 391-394. [10] Hermann J. et al. (2006) Lithos,
Fig. I) the magenta phase is lying in between the red 92,399-417. [II] Frezzotti M. and Ferrando S. (2007) Per.
arnet hase and the a ueous hase. Mineral. 76. 113-125. [12] Dobretsov NL et al. (1995),
Discussion: There are several possible mechanisms The lsI. Are, 4, 267-279. [13] Shatsky V. S. et ai. (1995),
explaining primary fluid inclusions and small scale Cambridge University Press, 427-455. [14] TheWlissen K.,
heterogenities in garnet composition associated with et ai. (2000) The lsI. Arc 9, 428-438. [15J Theonissen K. et
such inclusions. (i) True primary fluid inclusions, al. (2000), Ter. Nova, 12, 181-187. [16] Claoue-Long J. C.
which have formed during growth of garnet cores in et al. (1991) Geology 19, 710-713. [17] Shatsky V. S. et al.
the presence of fluid phase. The difference in the gar- (1999) CM?, 137, 185-205. [18] Hermann J. et al, (2001),
net compositions then appears due to the reaction be- CM?, 141, 66-82. [19] Ogasawara Y. et al. (2000). The
tween the fluid inclusions and the host-garnet. (ii) Island Are, 9, 400-416. [20] Korsakov A. V. et al. (2006)
Break-down low temperature and low pressure poly~ RGG, 47,497-510. [21] Perchuk A. L. et al. (2007). Lithos,
103,25-45
MOONSHOT: A COMBINED RAMAN I LffiS INSTRUMENT FOR LUNAR EXPLORATION. E. C. Laan',

4
W. van Westrenen 2, A. Wielders3, MJ. Heiligers 1 and MoonShot partners • ITNO Science & Industry, Space & Sci-
ence department, Stieltjesweg 1, P.O. Box 155,2600 AD Delf~ The Netherlands (erik.laan@tno.nl), 'vu University
Amsterdam, De Boelelaan 1085, 1081 HV Amsterdam, The Netherlands (wim.van.westrenen@falw.vu.nl), 'Space
Horizon, Duindoornlaan 24, 2015 LB Haarlem, The etherlands (arno@spacehorizon.com), 'Philips Applied Tech-
nologies, Delft University of Technology.
Introduction: Developments such as the rise of OR above the sample and an Electronic Assembly for
commercial so-called 'space travel' companies show instrument support and CCD readout. It is the first time
that the world is at the threshold of a new age of space that Raman spectroscopy and LIDS are combined into
exploration ('Space 2.0'). Coinciding with the transi- one miniaturized instrument with minimum mass, vol-
tion from Space 1.0 to Space 2.0, a new phase of com- ume and use of resources, a high spectral performance
mercial lunar exploration ('Moon 2.0') was initiated by and rapid analysis.
the announcement of the Google Lunar X Prize. The main science objective of the instrument on-
Participation in Moon 2.0 requires a new approach board a lunar mission would be to determine the min-
for conducting space projects as schedules are tight, eralogical and elemental composition of the lunar sur-
additional and non-traditional risks are involved, and face, to (a) provide details on the geological and geo-
new types of requirements are imposed on scientific chemical evolution of the Moon (b) perform detailed in
payloads. MoonShot is a project led by the Dutch Or- situ mapping of lunar material of interest for lunar ex·
ganisation for Applied Scientific Research TNO. with ploitation means and the realization of a future lunar
partners from industry and university planetary science base (c) demonstrate technology for future planetary
research centers in the Netherlands, that aims to pro- exploration missions and terrestrial spin·offs.
vide a combined RamanILIBS instrument as scientific
payload for planetary (e.g. Moon 2.0 lunar) exploration Current status: The RamanILIBS instrument was
missions. previously pre-selected as part of the ExoMars rover's
Pasteur payload and its end-to-end functional perform·
Instrument and Objectives: The RamanlLIBS in- ance has been demonstrated in an Elegant Bread Board
strument is a fundamental, next-generation instrument using natural samples under mission representative
for mineralogical and elemental (atomic) characteriza- conditions. Subsequently a Development Model (DM)
tion of lunar soil and rock samples. It uses an Optical of the spectrometer was built, which is intended to be
Head (OH) to illuminate samples with laser light that adapted (interfaces, temperature, atmospheric pressure,
generates physical phenomena (Raman shift and radiation, dust environment) for accommodation on a
plasma for the LIBS) with light emission. Emitted light lunar mission. As a resul~ parts of the RamanlLIBS
is collected and relayed to a spectrometer using optical instrument have a high Technology Readiness Level
fibres to record a spectrum on a CCD for sample iden- (TRL), while other subsystems (e.g. the DPM) have a
tification. Additional hardware components are a De- low TRL, expected to increase rapidly depending on
ployment Mechanism (DPM) to accurately position the specific mission boundary conditions.
Optical
fibres
Optical
Head
The IR Emissions of the mixed ice ofNH3+HzO+CH30H (1:1:1) induced by 15

+
keY H ion bombardemnt.
3
Chin Shuang Lee!, Wing Ipz, Chen Ning Chou!, Chen Wei Hwang!
3
Department of Physics!, Institute of AstronomyZ, Engineering, National Central
University, Jhongli, Taiwan 320

Email: cslee@phy.ncu.edu.tw
One of the assumptions the production of organic matters in the universe is originated
from the radiation of photo- and/or charged particle interacting with H2 0, NH3 ,
CH-bond, and other compounds contained in interstellar medium 0
In order to simulate the phenomena of solar wind interacting low-temperature plants,

such as Mars, in the earth laboratory. H 3+ ions are employed to irradiate ice of water
mixed with CH3 0H and NH 3• The technique used to identify and quantify the
synthesized species has been infrared spectroscopy. The experimental results are
discussed with a view to the relevance they could have in planetary environments
such as icy moons in the external solar system.
CL STUDY OF THE LOW·GRADE FELDSPAR ALTERATION.

J. Leichmann l and I. Broska2 , I Department of geological sciences, Faculty ofScinence, MU Brno, Czech Republic,
Leichman@sci.muni.cz. 2 Geological institute SAV, Dubravska cesta 9, 842 26 Bratislava, Slovakia,
Igor.Broska@savba.sk
Introduction: The aim of this work is to demon- tion is isochemical as well. The textural evidence indi-
strate how the CL method is able to detect the altered cates that calcite precipitate,s after prehnite. Such fea-
domains, and the migration pathways of fluids within ture indicate increasing amount of CO2 in primary pure
feldspars during the low-grade alteration of granitic aqueous fluids. The equation summarises the reaction
rocks. Altered granites with secondary Ca-AI silicates only schematically, It probably occurs in two steps: (i)
are a common object of mineralogical as well as ex- decomposition of primary K-rich oligoclase producing
perimental investigations [I], [2]. We present here white mica, prehnite and albite as a consequence of
results of microtextural and mineral-chemical investi- circulation of aqueous fluids and (ii) continuous de-
gations applying CL, EMP, including X-ray mapping, composition of plagioclase and precipitation of calcite
on plagioclases replaced by prehnite, albite, white instead of prehnite indicating increase of CO 2 in the
mica and calcite, from the West Carpathian granites fluids. Actually, both reactions must be considered as
[3]. . only schematical "whole rock". Cleavage seems to by
Analytical methods: Polished thin-sections were the main pathway, which brings fluids into the crystal
analyzed using the hot cathode HC2·LM apparatus at interior. The cleavage plain is filled by secondary
the Masaryk University in Brno. Accelerating voltage phases e.g. prehnite or calcite commonly. The altera-
was 14 kV and Current density 10·40 ltA! mm2. Elec- tion widens concentric from these plains. In many of
tron microprobe analyses of selected grains, and X-ray our samples, the inclusions of tabular white mica seem
to serve as a sort of barrier, which stopped the fluid
mapping were carried out with the Cameca SX 100
migration and protected a part of the grain from altera-
instrument in the wavelength-dispersion mode at the
tion. The white mica itself is not altered because of
Department of Geological Sciences MU Brno.
secondary white mica forms during alteration, so the
Results: Infiltration of simple aqueous fluids into
rock is inside the stability field of white mica during
the granite introduce a reaction plagioclase+K-
the alteration. Thin, open cracks were probably an-
feldspar+water = albite + prehnite +muscovite +
other channels that brought fluids to the central part of
quartz. The both reactants as well as products exhibit
the grain. Some of them are filled with secondary cal-
typical CL shade and could be easily identify using hot
cite with typical orange CL. Very fine grains of calcite
CL. The following EMP analyses and mainly X-ray
distributed along grain boundaries indicate that the
mapping enable us to detect element mobility during
fluids could penetrate the rock along grain boundaries,
the alteration even within one grain. This alteration
and if meet an open crack or a cleavage plain they en-
causes strong redistribution of elements within the
ter the grain interior too, and generate the alteration in
grain at different levels. Relics of primary andesine
the central part of the individual grains. In both cases,
rimmed by prehuite, which is closely associated with
only the An-richest domains were affected by altera-
albite, could document relatively small-scale element
tion.
redistribution (few microns). Evolved alteration leads
References: [I] Freiberger, R., Hecht, L., Cuney,
to the formation of domains by pure prehnite that are
M. & Morteani G. (2001) Contr. Miner. Petro 141: 415
more or less separated from zones fomed by albite
- 429. [2] Leake. B.E. (J998) Min.Mag. 62, (3): 381-
and secondary muscovite, indicating separation of Na
386. [3] Leichmann, J., Broska, I. & Zachovalova, K.
and K from Ca and migration ofNa and K and Ca over
(2003) Terra Nova 15 (2): 104-108
a distance of about 200 I'm within the grain. The fluids
with certain CO2 content cause slightly other reaction:
oligoclase (with minor orthoclase component) + water Acknowledgements: The research was support by pro-
+ carbon dioxide = albite + calcite +prehnite + white jects MSM 00216222416 and GACR 205/1159/06.
mica. The major difference to first reaction is massive
occurrence of calcite on the product site. This feature
requires presence of CO 2 on the reactant side, together
with H 20 needed for white mica and prehnite. The
amount of white mica is lower, comparing with the
previous grain. The source of K for white mica pro-
duction seems to be only the K contained in primary
plagioclase, which could be up to 1.1 wt %. The reac-
DECODING ENVIRONMENTAL CONDITIONS DURING SILICIFICATION OF PLANT STEMS

IN EQUATORIAL PANGAEA A D OMAN BY CATHODOLUMINESCENCE IMAGING AND
ANALYSIS. P. Matysova'~', J. Gotze " G. Forbes', J. Leichmann', R. RoBler' and T. Grygar'
'Institute of Rock Structure and Mechanics, ASCR, v.v.i., V Holesovickach 41,18209 Prague 8, Czech Republic;
*e-mail: pmatysova@email.cz;matysova@irsm.cas.cz. 2Institute of Geology and Palaeontology, Faculty of Science,
Charles University, Czech Republic, 'TV Bergakademie Freiberg, Germany; goetze@mineral.tu-freiberg.de,
'Petroleum Development Oman, Muscat 113, Sultanate of Oman; gordon.forbes@pdo.co.om, 'Masaryk University,
Brno, Czech Republic; leichman@scLmunLcz, ~useum flir Naturkunde, Chemnitz, Gennany;
roessler@naturkunde-chemnitz.de, 'Institute of Inorganic Chemistry, ASCR, v.v.L Rei, Czech Republic;
grygar@iic.cas.cz
Introduction: Our research of silicified stems from previous studies [1,2,3]; it follows that
from different localities around the world has been silicification is a very complex process which most
inspired by initial hot cathodoluminescence (CL) probably relates to different mechanisms, related to
studies on silicified Penna-Carboniferous plants from various original palaeoenvironmental conditions [6,7].
two localities in Germany: Thuringian Forest Basin, To clarifY CL signals in silicified plants and
e.g. [1], and Chemnitz Petrified Forest, e.g. [2,3]. understand the previous results better we have started
After a two year gap and despite the fact that to study samples from further 'test' localities with well
sedimentary authigenic quartz had been supposed to known geology that provide permineralized plant
have no or only very weak cathodoluminescence [4,5], stems of similar or different age. From an analytical
we used a similar methodology on Czech Upper point of view, we added high resolution scanning CL
Carboniferous material from alluvial deposits in the (HR-CL) imaging and hot CL spectroscopy to better
Intra Sudetic and Krkonose Piedmont Basins [6,7]. characterize the CL shades and reveal specific
The main aim was to extract more detailed information activators responsible for the signal. There is a chance
than mere palaeobotanical taxonomy because to interpret specific mineral characteristics that connect
a silicified stem, trunk, root, branch, and wood the plant bodies with past environmental and burial
represent a really unique association between fossil conditions [unp,ublished data].
plant and mineral phases. Our approach is based on According to our results, alluvial and
a combination of hot CL with other instrumental volcanoclastic environments of silicification
techniques (PPL, XPL, RL, SEMIEDS or WDS, and mechanisms/pathways are very different and that
XRD). The data obtained were surprising; CL variance is recorded in s·pecific composition
microscopy proved to be an unrivalled technique of silicified stems. Identification of SiO, polymorphs,
to distinguish primary and subsequent stages carbonates, phosphates, fluorite, clay minerals and
of silicification in samples from fluvial or possible allochthonous components help to understand the
lacustrine sediments and thus proved a multi-phase process because such mineral phases record the
process of silicification within the basin. Hot CL geochemical conditions during all stages
microscopy revealed detailed anatomical and of silicification.
petrographical features not seen by other microscopic Fossils from alluvia, mostly fluvial facies, such as
techniques. and also allowed the recognition of FexOy those from the Intra Sudetic, Krkonose Piedmont and
and allochthonous detrital grains. On the basis of West and Central Bohemian Basins (Czech Republic),
distinct CL shades, we suggested two different Tocantins (Brasil), North Cliffs (Sultanate of Oman),
schemes for CL interpretation; a petrographical one Autun (France), Arlit (Niger), showed mainly
related to morphological types ofSiO, crystals (each brownish, reddish and bluish CL shades, of a stable or
SiO, type gives a characteristic CL shade) and short-lived nature, lacking relatively high-temperature
a genetic one that is based on the existence of a short- mineral phases.
lived blue CL, which suggests more than one phase of Fossils from localities highly (Chemnitz, Germany;
silicification [6]. Fossils were permineralized mostly Petrified Forest NF, Arizona; Jumbi province,
by highly crystalline SiO, (quartz, proved by XRD), Sumatra, Indonesia) or slightly (Antarctica; Mongolia;
often with allochthonous material, in fluvial sediments, Balka, Czech Republic) influenced by volcanism often
and more variable silica mineralogy in specimens exhibit best preserved plant anatomy, and both SiG,
fanned by burial in volcanoclastics. Overprints and minor minerals often allow very detailed CL
of recrystallization were evident in almost all samples imaging. Hydrothermal secondary quartz is present as
and reflected a multi phase process of silicification a consequence of later burial diagenesis. Prevailing CL
in another way. Our CL results differ significantly shades are reddish and bluish, but also brownish and
yellowish. Fluorite (intensive bright bluish CL)

is a common component only in Chemnitz specimens.
Opal-CT and moganite were found in some Mesozoic,
Le. younger, specimens, but also in Permian specimens
from Chemnitz, but always in association with
volcanic material. Moganite and goethite were present
in Permian Omani samples from the vicinity of Saiwan
[unpublished data]. We try to answer the question
what caused the presence of moganite in the Omani
wood where no volcanic activity has been evidenced
until now. However, all pathways producing rnoganite
are not known at present time.
In summary, silicified stems must be considered as
unique and specific palaeo-environmental indicators.
The cathodoluminescence technique can help to
decode hidden characteristics in plant fossils that were
permineralized by silica and substantially contribute to
our understanding to palaeoenvironment, taphonomy
and stratigraphy.
Acknowledgement: This work is mainly supported
by the Grant Agency of ASCR (project No.
KJB301110704) and MSM0021620855.
References: [I] RoBler R. and Barthel M. (1998)
Freiberger Forsch.-H.C, 474, 59-101. [2] Gotze J. and
RoBier R. (2000) Veroff. Mus. Naturic Chemnitz, 23,
35-50. [3] Wilke K. et al. (2004) Spectrochimica Acta
A, 60, 2903-2912. [4] Gotze J. (2000) Freiberger
Forsch.-H. C, 485. [5] Boggs et al. (2002) 1. Sediment.
Res., 72,408-415. [6] Matysova P. et al. (2008) Eur.
1. Mineral., 20, 217-23 I. [7] Menel V. et al. (in print)
Neues.1.ahrb. Geol. Palaontol.-Abh.
Figure on the right: Arborescent tree fern

Psaronius sp. (# DS 6/98; Museum fUr Naturkunde,
Chemnitz, Germany); Comparison of different
microscopy imaging techniques: PPL, XPL, and CL.
CL can highlight tiny anatomical and petrographical
details in a part of an adventitious root from the inner
root mantle. Yellow CL is typical ofChemnitz locality.
Legend: sc - sclerenchyma, me - mucilage canals, vs -
vascular strand, Seh - spherulitic chalcedony creating
agate-like structures in the root matrix.
CATHODOLUMINESCENT FEATURES AND RAMAN SPECTROSCOPY OF MIOCENE

HYDROTHERMAL BIOMINERALIZATION EMBEDDED IN CRYPTOCRYSTALLINE SILICA
VARIETIES, CENTRAL EUROPE, HUNGARY A. Mlillerl, M. Polgari', A. Gucsik', Sz. Nagy', M. Veres', E.
Pal-Molnar', J. Gotze', C. Cserhati', T. Nemeth', M. Hamor-Vid6', 'Szeged University, Dept. of Mineralogy,
Geochemistry and Petrology, 6702 Szeged, Egyetem str. 2-6, Hungary, basmacskin@gmail.com, 'Institute for
Geochemical Research, 1112 Budapest Budaorsi str. 45, Hungary, rodokrozit@gmail.com, 'Max Planck Institute
for Chemistry, Dept. of Geochemistry, Joh.- J. Becherweg 27, D-55128, Mainz, Germany, gucsik@mpch-
mainz.mpg.de, 'ElilVos University, Faculty of Science, Institute of Physics, Dept. Material Physics, H-1117 Buda-
pest, Pazmany Peter serany Ila, Hungary, ringwoodit@yahoo.com, 'Research Institute for Technical Physics and
Material Sciences, H-1121 Budapest, Konkoly-Thege M. str. 29-33, Hungary, vm@szfki.hu, 'Tv Bergakademie,
Freiberg, Department of Mineralogy, Gennany, goetze@mineral.tu-freiberg.de, 7University ofDebrecen, Faculty of
Science and Technology, Dept. of Solid State Physics, Debrecen, Bern ter 18, Hungary, cserhati@delfin.klte.hu, '
Eotvos Lorand Geophysicallnstitue, 1145 Budapest, Kolumbusz str. 17-23, Hungary, vido@elgi.hu.
Introduction: At the southern part of the Matra bially mediated way of explanation for the studied
Mts. (Hungary), in the neighborhood of Gyongyostar- Miocene hydrothermal vent fonnation was raised and
jim and Gyongy5soroszi area, variable cryptocrystal- proved for the first time. The signs of microbial activ-
line silica varieties occur en masse in the fractures and ity are supported hy the weathering formation of the
cavities of the andesite host rock near the surface [1]. host andesite, the variable and numerous rock var-
The great variety of colour and morphology is caused nishes on their surface. microbial fonns (filamentous,
by the different genetic and morphological features of coccoid and microcolonial fungi type), and the textural
variable microbial (bacterial and microcolonial fungi features of the silica matrix, which genetic processes
type) activity and interaction with inorganic hydro- were modelling. The small and uniform grain size
thennal vent system, which have embedded in crypto- (phase dimension), the chemically poor occurrence
crystalline silica matrix. The aim of this research is the also support the biogenic origin as well as the often
characterisation of cathodoluminescent features of occurring curved morphology and variable "large for-
biomineralization products occurring in the samples, mats" built up from the same small units.
and the detennination of the form of 1-3 wt. % carbon The fluorescence study showed the remnants of or-
content, giving further evidences of microbial contri- ganic matter in the samples occurring by greenish yel-
bution. low colour (Fig. I).
Samples and methods: 150 polished surfaces and 83 The electron-microprobe analyses determined 1-3
thin sections were investigated by rock and optical wt. % C content in the silica matrix and in mineralized
microscopy (reflected and transmitted, Nikon Eclipse forms (Fig. 2). In a selected sample the inner mineral-
600 microscope), and selected samples by ized filamentous microbial part is composed of 47.8
cathodoluminescence (Reliotron cold cathod), wt. % Si, 2.1 wt. % Fe, 0.6 wt. % AI, 0.2 wt. % Mg,
fluorescence (Leica DM-RX research microscope), 0.5 wt. % K, 0.2 wt. % Ca and 1.6 wt.% C on average
methods. X-ray powder diffraction measurements were (selected elements). The content of the supposed min-
carried out on 10 selected samples for detennination of eralized extracellular polymeric substance around the
mineralogical composition (Philips PW 171O). filamentous forms is 37.9 wt. % Si, 8.1 wt. % Fe, 0.8
Electron-microprobe analyses were made to detennine wt. % AI, 2.6 wt. % K, 0.4 wt. % Ca, 0.7 wt. % Mg,
element distribution and textural features on 8 thin 0.1 wt. % a and I.5 wt. % C. The silica matrix is
sections (Nikon Eclipse 600 Hitachi S4300-CFE SEM composed of 45.7 wt. % Si, 0.3 wt. % AI and 2.4 wt.
with Broker Quantax, XFlash 4010 detector). %C.
Additionally, the structural properties of the selected Deep purple, red dull cathodoluminescence of the
minerals were detennined by a Renishaw-l 000 Raman microbial textures were often observed in the thin sec-
spectrometer, the laser wavelenght was 785 nm, with tions (Fig. 3). According to electron microprobe meas-
focused energy of 8 mW. The maximal focus was
urements these phases are Fe and Si rich.
driven to 1 J1m spot in diameter. The thin sections Spectroscopic characterisation of the cathodolumi-
were mounted in epoxy material, and the sample
nescence of biomineralization products is in progress.
thickness is 30 flm. Cathodoluminescence results also showed the fonna-
Results: Detailed detennination and description of tion of silica phases on different temperature condi-
textural features of the samples showed signs of com-
tions, which was probably caused by the oscillating
plex microbial and inorganic interactions. The micro-
60 LP1 Contribution No. 1473
temperature geyser and vent activity in the surrounding spectra (Fig, 4) [2]. The broad bands of the latter phase
environment. indicate amorphous carbon phases.
Fig. 3. Cathodoluminescence of mineralized fila-

mentous microbial fonns
Fig. J. Thin section (a, IN) and fluorescence photo

(b) of biomineralization products
250 500 750 1000 1250 1500 1750 2000
l
Raman shift [crn' J
Fig. 4. Typical Raman spectra measured in the area of

mineralized filamentous microbial fonns.
Conclusion: Dull purple red cathodoluminescence

and greenish yellow fluorescence of variable biomin·
eralization products embedded in cryptocrystalline
silica matrix were observed. Electron microprobe ele-
ment measurements showed Fe-rich silica phases, with
1-3 wt. % C, and in most cases less that 1 wt.% trace
element contents (AI, Ca, Mg, K) for the samples. The
Fig. 2. BE! of mineralized filamentous bacterial occurrence of amorphous carbon phases in the samples
forms (light phase) in cryptocrystalline silica matrix. can be further evidences of microbial origin, and/or
might be connected with hydrothermal contamination
XRD mineralogy of the samples consists of opal processes, which could serve as organic nutrients for
CT, quartz, goethite. hematite. nontronite, and cela· heterotroph microbes in the system. This is also sup-
donite. ported by the presence of moganite, which was found
Raman spectroscopy was also used to study the to fonn in the surrounding of organic carbonaceous
products of biomineralization. Characteristic peaks of phases [3]. Spectral characterisation of cathodolumin-
calcite (at 1085 em"), hematite (at 226 and 608 em"), scence is proceeded.
goethite (at 298, 385, 438 and 548 em"), a-quartz (at References: [I] Czak6 T. and Zelenka T. (1981)
261, 353, 393, 462, 463 and 801 em"), moganite (at Advances in Space Research, 1,289-298. [2] Kuebler
501 cm'l) and different carbonaceous materials (at et aI., (2006) LPSC XXXVII, # 1907 [3] Kovacs Kiss
1340, 1380, 1548 and 1572 em") were found in the V. (2000) PhD thesis.
Evidence of Shock Metamorphism in Hungarian L-chondrites using Raman Spectroscopy. Sz. Nagy!, A.
Gucsik2, Sz. Berczi l, M. Veres3, 1. Gyollai l , J. FiiIjl IEotves University, Faculty of Science, Institute of Physics,
Dept. Material Physics, H-1117 Budapest, Pazmany Peter setany 1/a, Hungary, 2Max Planck Institute for
Chemistry, Dept. of Geochemistry, Joh.- J. Becherweg 27, D-55128, Mainz, Germany, 'SZFKI-KFKI, H-1121
Budapest, Konkoly-Thege M. ilt 29-33.
Introduction: The M6cs and MezOmadaras PDF's lamellae, the other points (Mocs II.) was in
meteorites felt in 1882 and 1852, respectively. The between PDF's (Fig. 2).
M6cs meteorite is an L5 and MezOmadaras is an
L3-type chondrites. The chemical composition of
these samples were determined the Electron
Microprobe Analyses (1]. The shock-metamorphic
classification of M6cs and MezOmadaras meteorites
were classified as S3-S5 for Mocs, and S2-S3 for
Mezomadaras by Optical Microscope [2]. We have
reinvestigated of these samples using Raman
spectroscopy for the identification of any shock-
metarnorfic effects occured in the structure changes
of olivine and pyroxene grains. The detailed OM
analyses show mechanical twins in pyroxenes (Fig.
I), planar fractures (PF's), and planar deformation
features (PDF's) (Fig. 2). Furthermore shock
mosaicism in olivine grains is also discernible (Fig. Fig. 2 Places of two points for raman
3). !'he Raman spectroscopical investigation spectroscopical analysis in PDF's rich olivine grain
revealed ~-(Mg, Fe) SiO, olivine structure from Mocs meteorite. Reflected light micrograph
(wadsleyite) in a PDF's enriched and highly image.
deformed olivine grain.
The characteristic Raman peaks of Mocs I are: 630
Samples and Experimental Procedure (strong-s), 706 (medium-m), 722 (very weak-vw),
The mineral assemblages and textures were 751 (weak-w), 852 (very strong-vs), 883 (very
characterized by a Renishaw-lOOO Raman stroog-vs), and 987 (strong-s) cm· l . The Mocs Il-
spectrometer, the laser wavelenght was 785 nm. spectrum contains the following peaks: 421 (s),577
with focused energy of 8 mW. The maximal focus (m), 642 (w), 822 (vs), 854 (vs), 920 (m), and 958
was driven to lllm spot in diameter. The thin (m) cm<I, We used a reference material from the
sections were mounted in epoxy material, and the Trudy's mine olivine to the comparison with the
sample thickness is 30 J.lm. vibrational changes of our spectra (Fig. 4). Note
that the spectrum was derived from CALTECH
Raman database. The most characteristic changes in
the Mocs I-spectrum are. The olivine doublet peak
position is shifted to higher wavenumbers, due to
partly disordered olivine structure. The doublet
peak's shift was also observed in olivine
(crystalline forsterite) experimentally shocked
between 0-50 GPa [3]. The second important
change in the M6cs I-spectrum is in the middle
wavenumber region. The olivine structure
vibrations are forbidden in this region. The 751 cm-
I peak is assigned to the presence ofSi-O-Si bridges
characteristic of wadsleyite [3,4] indicating the
highly deformed olivine structure [2]. Tbe 722 cm· l
Fig. I Optical microscope (cross-polarised) image peak belongs to the wadsleyite Si 20, symmetric
of pyroxene with mechanical twins in stretching vibrational mode [5,6]. However, the 918
MezOmadaras meteorite. cm-l peak is not identical to the wadsleyite SiO)
symmetric stretching vibrational mode, because of
Results and Discussion the doublet peak position.
Mocs meteorite: In a highly deformed and PDF's Mezomadaras meteorite: MezOmadaras sample
enriched olivine grain was selected for the Raman contains poikilitic pyroxene condrums, which show
investigations representing two analyzing points, as elongated shape. Within these condrums, the
follows. The first point (Mocs I.) was placed on the pyroxenes have mechanical twins.
FWHM rate in meteorites can be due to shock-

metamorphic mechanism.
Fig. 5. Raman spectra of pyroyenes from different

Fig. 3. Moderately mosaiCIsm in olivine from sources.
Moes sample. OM-image
On the basis of the measured FWHM, the following
Within the most common (Mg-Fe-Ca) pyroxenes structural disordering degree of the selected
we can distinguish more than ten Raman active samples can be detennined as a (growing rate):
vibrational modes [7]. The four spectra (Fig. S) Castle Rock, Meromadaras, Shergotty and Moes.
show different chemical composition between the The result reveals that amorphisation rate is the
Castle Rock (as a reference spectrum) and three highest in Moes and Shergotty pyroxene grains.
meteorites sample. The Mocs spectrum have the
following peaks: 368 (vs), 426 (5), 475 (m)?, 693 Conclusion
(vs), 710 (vs), 1040 (vs) cm,l The Mez6madaras This study demonstrates that the micro-Raman
spectrum contains peaks: 372 (5), 475 (w)?, 694 spectroscopy can aid to understand about the study
(vs), 716 (vs), and 1041 (vs) em". The of shock-induced phase transformation and range of
characteristic peaks of Shergotty pyroxenes are: structural disordering in minerals from various
359 (vs), 426 (vs), 567 (vw), 590 (vw), 698 (vs), meteorites.
and 1043 (vs) em". The Castle Rock pyroxene
exhibits the following peaks: 340 (vs), 402 (s), 439 Acknowledgement
(5),538 (m), 661 (vs), 682 (vs), 860 (m), 936 (w), We are grateful for Professors I. Kubovies for
and 1009(vs) em". helpful discussions, and for Raman Laboratory of
SZFKl (Budapest, Hungary) for instrumental
background.
References
[I] Kubovies et aI., (1997) NIPR Symposium,
Tokyo pp. 13-14.
[2] http://www.museum.hu-berlin.de/min/forsch/
Sehoekklassifikation%20StoeffierlFinal%20Versio
n/subdir/lisl.htrn [3] Durben et aI., (1993) American
Mineralogist, Volume 78, pp. 1143-1148. [4] Gillet
Fig. 4. Raman spectra of olivine in Mocs meteorite et aI., (2005) Meteoritics & Planetary Science 40,
sample. pp. 1175-1184. [5] Kleppe et aI., (2006) American
Mineralogist, Volume 91, pp. J 102-1109. [6]
The degree of the structural disordering was Kleppe et aI., (2002) Physics and Chemistry of
determined by FWHM (Full Width at Half Minerals, 29, 376-473. [7] Huang et aI., (2000)
Maximum) values. Under the 500 em" range the American Mineralogist, Volume 85, pp. 473-479,
Moes sample, has the highest rate of FWHM as 17
em" but the Castle Rock sample shows 11 em".
The Meromadaras and Shergotty samples are
between two of the above mentioned samples
(FWHM rate is 15 em"). This indicates the
significant changes in the Si-O stretching modes
and SiO. tetrahedra rotational modes. Above 800
cm- 1 range, the FWHM rates are: Mocs 21 em-I),
Shergotty 20 em"), Mez6madaras 18 em"), and
Castle Rock 15 em"). These data represent higher
structure disordering degree in meteorites than in
the terrestrial Castle Rock sample. The higher
Conference Of! Micro-Raman Spectroscopy and Luminescence Studies 63
THERMOLUMINESCENCE STUDY OF ORDINARY CHONDRITES. K. Ninagawa, Department of Applied

Physics, Okayama University of Science, 1-1, Ridai-cho, Okayama 700-0005, Japan (ninagawa@dap.ous.ac,jp)
Introduction: Thermoluminescence (TL) is light tral peaks at 440 nm and 400nm, and 170 and 360'C,
emitted by a phosphor in addition to intrinsic black- respectively. The mineral responsible for the both TL
hody radiation during heating [1-2]. There are two peaks is sodic plagioclase in the ordinary chondrite. In
types of TL measurements: natural and induced TL. the usual TL measurements using a photomultiplier,
Natural TL is luminescence of a sample that has re- ultraviolet-blue region have been detected with Corn~
ceived no irradiation in the laboratory. Then it reflects ing 4-69 and 7-56 filters. The induced TL glow curve
the thennal history of the meteorite in space and on is characterized by peak temperature, peak width, and
Earth. Natural TL data provide insights into such top- TL sensitivity (normalized by TL intensity ofDhajala).
ics as meteoroid orbits, shock heating effects, and ter-
restrial histories of meteorites [3-4]. Induced TL is the ..... ~,,~ ,,~, .... lUI
response of a luminescent phosphor to a laboratory

dose of radiation. Then it reflects mineralogy and
structure of the phosphor while providing valuable
- ,._><
infonnation on thermal and shock metamorphism of
meteorites. A great work for chondrites by TL method ...... ,.
,,,
---'-r'
was discovery of wide induced TL sensitivity variation l~
of type 3 ordinary chondrites, and relation to thermal "
metamorphism [5]. The mineral responsible for the TL l~.·
in the ordinary chondrites is mainly the sodic plagio-
clase. Thermal metamorphism on parent bodies pro- ,1~
duced sodic plagioclase from feldspathic glass with 1·"
devitrification [6J. According to this, the induced TL j
sensitivity of petrographic types 3 ordinary chondrites
has been introduced as an important indicator for clas- Figure 1. Induced TL spectra of Bjurbole (U, SI).
sifying them into subtype 3.0-3.9 with olivine hetero- The abscissa is wavelength (nm), and the ordinate is
geneity [7]. temperature CC). TL intensity is displayed by false
National Institute of Polar Research (NIPR, Japan) colors.
takes 16,201 meteorites from Antarctica so far [8J. SO
far the TLs of eighty-two Yamato and ninety Asuka The TL properties of ninety Asuka type 3 ordinary
type 3 ordinary chondrites in the Japanese Antarctic chondrites in the Japanese Antarctic meteorite collec-
meteorite collection have been measured for subtype tion have been measured. Most of the samples had TL
detennination [9-12]. sensitivities over 0.1, corresponding to petrologic sub·
On the other hand, the minerals responsible for the type 3.5-3.9. Twenty-one chondrites have very low TL
TL in low thermal metamorphic grade (primitive) or- sensitivities under or near 0.1. Primitive chondrites of
dinary chondrites are not only sodic plagioclase but petrologic subtype ~ 3.4 have coefficient of variations
also anorthite-nonnative mesostasis, iron-free enstatite, (0' as a percentage of the mean) over 50%, of fayalite
and silica phase [13-16J. TL emission spectra of anor- in the olivine [7]. Eleven chondrites, A-881607 (LU),
thite-normative mesostasis and iron-free enstatite were A-881328 (LL3), A-88l408 (LL3), A-881397 (LU),
yellow and red, respectively. A-881199 (LU), A-881357 (LL3), A-9046 (LL3), A-
881244 (U), A-873l9 (U), A-9043 (L3), and A-
TL of Type 3 Autarctic Ordinary Chondrites: 881522 (U) satisfied coefficients of variation over
Meteorites over 2000 fragments were collected by 50%, as shown in figure 2. They are primitive ordinary
Japanese expedition from dirt bands south of the S0r chondrites.
Rondane Mountains near Asuka station (S71 0 31 134!! Residual ten chondrites, however, have coefficients
E24 '08'1 7") in Antarctica. Figure 1 shows the induced of variation under 50% with the inconsistency between
TL spectra of ordinary chondrites. There are two spec- TL sensitivity and olivine heterogeneity. TL sensitivity
decreases 10-fold after shock-loading to 25-32 GPa red TL had been outside of the detection wavelength in
[17]. and terrestrial weathering makes TL sensitivity usual TL measurements with Corning 4-69 and 7-56
decrease l6-fold at maximum in Antarctic chondrites filters. The yellow cathodoluminescence (CL) and red
[18]. These chondrites, surrounded by solid rectangle CL were also observed from the same specimens. Sil-
as shown in Figure 2, might suffer remarkable shock ica phase was also responsible for the TL in ALH-
and/or terrestrial weathering. 77214 (LL3.4) [16].
10
o Asuka H3
o Asuka L3
6. Asuka LL3
,
in
0
~
~
l, .;:;w" ...... ".. ......,."
~ .. _. .. ,,,.
....
Figure 3. TLspectra ofSemarkona (LL3.0) includ-
··;',c ~·"'m
A·II"" ing a type I chondrule.
A."""
I, _t:,;m References: [1]Aitken M.J. (1974) Physics and ar-
..... "...
I 11""";.. ,,~ II chaeology. Clarendon Press. [2]McKeever S.W.S.
0.01
..... ,,'" --,..
...... , (1985) Thermoluminescence of solids. Cambridge
University Press. [3]Benoit P. H. et a!. (1991) Icarus,
94,311-325. [4]Benoit P. H. et a!. (1992) J. Geophys.
,..,.,,:u
...-
b.
...... 111
,.. Res., 97, 4629-4648. [5] Sears D. W. G. et aJ. (1980)
I I I
Nature, 287, 791-795. [6] Sears D. W. G. (1988) NucJ.
0.001
~Crl Tracks Radiat. Meas., 14, 5-17. [7] Sears D. W. G. et
aJ. (1991) Proc. Lunar Planet. Sci., 21, 493-512. [8]
1% 10% 100% Kojima H. et aJ. (2008) Meteoritics & Planetary Sci-
Olivine Heterogeneity (C.Y.)
ence 43, No.7 Supplement, A184. (9] Ninagawa K. et
Figure 2. Dhajala-normalized TL sensitivity vs. oli- aJ. (1998) Antarct. Meteorite Res., II, 1-17. [IOJ Ni-
vine heterogeneity of Asuka ordinary chondrites. Type nagawa K. et al. (2000) Antarct. Meteorite Res., 13,
3 chondrites with coefficients of variations under 50%. 112-120. [II J Ninagawa K. et aJ. (2002) Antarct. Me-
of fayalite in the olivine and TL sensitivities under or teorite Res., 15, 114-121. [12] Ninagawa K. et al.
oear 0.1 (Dhajala=l) are surrounded by solid rectangle. (2005) Antarctic Meteorite Res., 18, 1-16. [13] Nina-
gawa K. et al. (1992) Proc. NIPR Symp. Antaret. Me-
TL of Primitive Ordinary Chondrites: Primitive teorites, 5, 281-289. [14] Matsunami S. et a!. (1993)
ordinary chondrites have been considered to have the Geochim. Cosmochim. Acta 57, 2101-2110. [15]
lowest TL sensitivity, hased upon the TL petrologic Ninagawa K. et aJ. (1994) Proc. NIPR Symp. Antarct.
classification. However, intense TL glow curves were Meteorites, 7, 217-224. [16] Matsunami S. et aI.,
observed in Semarkona (LL3.0), Bishunpur (LL3.1), (1992) Proc. NIPR Symp. Antaret. Meteorites, 5, 270-
Chainpur (LL3.4), and ALH-77214 (L3.4) It was 280. [17] Hartmetz C. P. et al. (1986) Proc. 17th Lunar
found that anorthite-nonnative mesostasis in type I Planet. Sci. Conf. (J. Geophysical Research), 91,
chondrule showed TL with a spectral peak at 570 nm E263-E274. [18] Benoit P. H. and Sears D. W. G.
(Fig. 3) [13-14], and iron-free enstatite showed TL (1999) J. Geophys. Res., 104, 14159-14168.
with a spectral peak at 660 nm [15J. Such yellow and
Cathodoluminescence microcharacterization of ballen silica in irnpactites. T. Okumura l , A. Gucsik2, H. i-

shido 1 and K. Ninagawa J, lResearch Instimte of Natural Sciences, Okayama University of Science, 1-1 Ridai-cho,
Okayama 700-0005, Japan, E-mail: okumura@rins.ous.ac.jp; 'Max Planck Institute for Chemistry, P. O. Box 3060.
D-55020 Mainz, Genuany; 'Department of Applied Physics, Okayama University of Science. 1-1 Ridai-cho, Oka-
yama 700-0005. Japan.
Introduction: The physical state of silica is a very Consequently, CL microscopy and spectroscopy
useful index for shock-metamorphism [I]. In this study, are an easy and powerful technique for identifying
we used cathodoluminescence (CL) microscopy and silica polymorphs in ballen, and CL investigation
spectroscopy to characterize balleo silica structure. provides a new knowledge due to clarify the fonnation
"Balleo silica", characterized by bubble-wall texture mechanism of ballen silica.
under a petrological microscope, has been observed in
impactites [2-4). Bischoff and St6ffler (3) found that
ballen silica represents recrystallized diaplectic glass
that had undergone the transition to cristobalite and
then to a-quartz.
Samples: The ballen silica samples were obtained
from six terrestrial impact craters; Dellen, Mien (both
Sweden). Lappajarvi (Finland), Rochechouart (France).
Temy (Ukraine), and Ries (Genuany).
Analytical Procedures: CL measurements were
done on carbon-coated, polished thin sections. Color
CL imaging was performed on a CL microscope. The
system was operated at 15 kV accelerating voltage and
a-qUo!lrtz + a-cristobo!llite
a beam current of 0.5 rnA. CL colour images were cap-
tured using a digital photomicrographic camera system.
High-resolution CL images and spectra were acquired
using a scanning electron microscope (SEM) equipped
with a grating-type monochromator, SEM-CL system. a-quartz
This system was operated at 15 kV accelerating volt-

age and a probe current of 1.5 nA. CL spectra were
recorded in the wavelength range of 350-750 om with
1 nm spectral resolution and a dwell time of 1 second 400 500 600 700
per step by photon counting. Wavelength (nm)
CL Characteristics of Ballen Silica: The Ballen Figure 2. CL spectra of ballen silica from Lappajarvi
silica shows fairly weak (faint) CL with homogeneous crater, Finland.
feature in its grain (Fig. I). Ballen silica samples ex-
hibit almost same spectral pattern with two broad band References: [1) French B. M. (1998) LPI Contri.
peaks at around 390 and 660 nm (Fig. 2), which might #954, 120pp. [2) Carstens H. (1975) Contri. Mineral.
be assigned to self-trapped excitons (STE) or an intrin- and Petrol., 50, 145-155. (3] Bischoff A. and SlOffler
sic and nonbridging oxygen hole centers (NBOHC), D. (1984) J. Geophys. Res., 89, B645-B656.
respectively, recognized in amorphous and crystalline [4] Ferriere L. et a!' (2008) Large Meteorite Impacts
silica [5]. In addition, ballen silica from Lappajarvi and Planetary Evolution IV, Abstract #3011. (5) Ste-
crater shows bright and heterogeneous CL with a broad vens Kalceff M. A. and Phillips M. R. (1995) Phys.
band centered at around 410 om (Fig.2), presumably Rev. H52, 3122-3134. [6] G6tze J. et a!' (2001) Min-
attributed to a self-trapped exciton (STE) or an intrin- eral. and Petlor.7!, 225-250.
sic [6]. Micro-XRD and micro-Raman analyses show Acknowledgements: We are grateful to M.
that fairly homogeneous CL part is ex -quartz and Schmieder and E. Buchner at University of Stuttgart
heterogeneous CL part is composed of ex -cristobalite who kindly supplied the rock thin section samples.
and a-quartz. These indicate that ballen silica could be Micro-Raman spectroscopy have been supported by M.
fonned in the quenching process from relatively high Sugiyama at Kyoto University.
temperature.
SPECfRAL AND MICROSCOPIC ANALYSES OF FOSSIL MICROORGANISMS IN A JURASSIC

OOLITIC LIMESTONE Y. Rubert l2 , C. Ramboz l , P. Gautret l , T. Dieing', F. Westall" D. Bonijoly', Y.M. Le
Nindre', C. Lerouge'. I: UMR 6113 and CNRS-ISTO, labis rue de la Ferallerie, 45071 Orleans cedex2 (France); ':
BRGM, BP609 45060 Orleans (France) y.rubert@brgm.fr; 'WITec, Ulm (Germany), 'CBM, Orleans (France)
Introduction: The Jurassic Plateau of l'Ile Cre-

mieu, north of the Cenozoic Valence Basin, hosts a A ...
dense karstic network. In the Loras quarry, flat-lying r1'~ ...
oolithic bajocian carbonates are crosscut by tw"o sets of
fractures, structurally compatible with the NNE-SSW
pyrenean compression [1]. These fractures are occa-
. '
sionally lined with open vugs, floored by rhombo-

hedral mm-sized calcite crystals. Cathodoluminescence
reveals three stages of calcite vein infilling. Two early
calcite generations fonn a discontinuous coating on the
fracture walls: early euhedral calcite I, orange in ca-
thodoluminescence (CL), is elongated parallel with the
fracture plane (Fig. IA). It is followed by isometric ',
euhedral calcite II with fIne orange CL bands (Fig.IA).
A late infIlling of calcite 1II that has no CL signature I
.~g-~
forms the main vug filling. The bajocian oolite is mas-
sively luminescent.
.. ~
,. --
~~--= - • •.
A dense filamentous microbial/fungal community
with a bright orange CL signature is anchored at a Fig. I: Photomicrographs of the vuggy calcite (CI
depth of 1-2 mm in the oolitic wall and emerges at to CIII) and associated micro-organisms: (A) CL and
right angle in the 'open' fracture space. It is particu- (B,C) under blue ligth after acridine orange staining;
larly well-preserved when embedded by the calcite I MFC= microbial/fungal community; EPS=. extracellu-
infIlling. lar polymeric substances. D to E : SEM images of the
Geological context: L'lIe Cremieu was part of the fIlament embedded in calcite (CM=cellular mem-
Mesozoic platform till the fInal emersion at the end of brane). G: Filament section (reflected light) and (H)
the Cretaceous. From the Tertiary to the present, it related confocal Raman mapping of the different car-
remained a continental platform [2] and was affected bon phases. (1) Three main characteristic organic mat-
by the Cenozoic tectonic events [I]. In particular, the ter spectra (in color; see text), and host calcite spec-
Pyrenean compression, which yielded the studied frac- trum (in grey).
ture sets, culminated at the Eocene. The sedimentary
cover over the vugs could not have exceeded a few Optical features. Two types of fIlaments are ob-
100 m [2]. The CL properties of the vein calcite, served associated with the fracture surfaces. Long,
evolving from bright orange near the fracture wall to branching fIlaments up to Imm in length and from 10-
non CL towards the center of the vug, indicates pro- 15 11m in diameter penetrate into the oolitic calcite up
gressive environmental changes from a midly reducing to depths of 2 mm from the fracture surface. Shorter,
environment that is contemporaneous with the coloni- stubby fIlaments, 300-~m in length and I0 ~m in di-
zation of the micro-organisms to oxidizing vadose ameter, fonn a "brush"-like layer on the fracture sur-
conditions in a continental setting [3,4]. Finally, the 0- face. The latter are embedded in the fracture surface
isotopic compositions of calcitic vugs of Pyrenean age and orientated outwards towards the "open" fracture.
from around the Valence Basin point out to a meteoric Filaments that are embedded in the wall-rock are fre-
origin of the depositing fluid. quently coated with Fe-Mn oxides, but only rarely so
when embedded in calcite. When excited at a blue
Preservation state of the micro-organisms: The wavelength, the filaments massively fluoresce in
state of preservation of the microorganisms was inves- green. Under UV light, they weakly fluoresce in white
tigated using different, independent imaging (fluores- and the outer rim of calcite I crystals displays a cloudy
cence microscopy, SEM) and analytical (EDS, confo- white fluorescence.
cal-Raman) techniques, both in the oolitic wall-rock Acridine orange staining (Figs. J B to Ie). Reaction
and in the vuggy calcite. with this dye is strongly positive over wide portions of
the filament surfaces, both in the wall-rock and in the carbonate adjacent to the filaments may represent mi-
fracture. The cloudy white portions of calcite I re- crobial dissolution features.
vealed under UV light also positively react with ac- Preservation of the filaments was by the precipita-
ridine. This indicates that active acidic polysaccharides tion of a calcite crust along the walls of the filaments.
(extracellular polymeric substances, EPS) are still pre- The presence of organic molecules within the calcite
served in the filament remains and in calcite I. The crust indicates that it incorporated cell-bound micro-
latter is therefore heavily loaded with EPS. bial EPS. The higher crystal organization of the rem-
SEM + EDS localized microprobe onaiyses (Figs. I D nant organic matter immediately adjacent to the calcite
to IF).. SEM images reveal the presence of numerous crust suggests that the presence of the latter may have
micropores in the carbonate matrix near the filaments influenced the crystallinity of the degraded organic
(Fig. lD). They show that the filaments are composed matter. The organic film lining the inside of the fila-
of aligned cells, sometimes with preserved organic ments, on the other hand, exhibits less crystallinity.
membranes. Where well-preserved, the cells are -30 Conclusion: A combination of imaging, spectral
~m in length and J 0 ~m in width and are separated analyses and spectral mapping documents the coloni-
from each other by a meniscus. Some filaments are sation of a fracture in oolitic limestone of two kinds of
surrounded by a continous sheath, locally displaying a rock-inhabiting microorganisms. Endolithic fungal
multilayered texture. A fringe of microcrystalline cal- hyphae penetrated deep into the rock whereas chemo-
cite systematically develops in contact with the micro- lithic filaments colonized the walls of the fracture.
organisms. EDS analyses confirm the carbonaceous They were encased by calcite and their remains further
nature of the sheaths and cellular membranes, enriched sealed and preserved by a number of episodes of cal-
in sulfur. cite infilling of the fracture.
Confocal Raman imaging and spectroscopy (Figs. References:
1G to 1H). Raman spectra show a C-H stretching [I] Rocher M. et a!. (2004) C.R. Geosciences, 336,
=
band at 2900 em·] and two additional bands in the 1209-1218. [2] Enay R. (1980) Soc. Lintienne Lyon, 8,
range 1580-1610 and 1350-1380 em·] (G and D bands, 482-505. [3] Emery, D. and Dickson, J.A.D. (1989)
respectively) which characterize disordered polycrys- Sedimentary Geology, 65, 273-284. [4] Horbury, A.
talline graphite [5]. The organic nature of the cells and D. and Adams, A.E. (1989) Sedimentary Geology, 65,
spectral mapping of these components document their 319-344. [5] Beny-Bassez, C. and Rouzaud, J.N.
distribution in association with the filaments. The or- (1985) Scanning Electron Microscopy, 1,119-132.
ganic matter in the wall of the filaments immediately
adjacent to the mineral matrix is more crystalline than
that towards the inner part of the filaments. Moderate
to strong fluorescence is also associated with the fila-
ments and the adjacent calcite matrix, confirming the
presence of organic molecules (EPS) within the min-
eral.
Discussion: Our observations indicate that there

are two kinds of infiltrations in the oolitic limestone:
(1) long filaments penetrating deep into the carbonate
that clearly demonstrate endolithic behaviour and re-
semble fungal hyphae; and (2) shorter filaments that
extended into the open fracture space. They can be
considered as chasmolitihic microorganisms since they
fonned at depth in the fracture. In this environment.
the filaments are not reliant on light and are therefore
not photosynthesizing microorganisms. On the con-
trary, their association with the carbonate in this habi-
tat suggests rather a chemolithotrophic metabolism.
Their source of electrons was probably H, possibly
obtained from the through-flowing fluids in the frac-
ture. CO 2 would have been available in the fluids from
dissolution of the limestone. The micropores in the
IN-SITU MICRO-R-\MAN AND MOESSBAUER SPECTROSCOPIC STUDY OF EVAPOMTE MINEMLS IN RIO

TINTO (SPAIN): APPLICATIONS FOR PLANETARY EXPLOMTION F. Rull', G. KlingelhOfer', A. Sansano', I.
Fleischer2 , P. Sobron l , M. Blumers2 , A. Lafuente l , D.Schmanke2, J. Mauf
lUnidad Asociada UVA-CSIC, al Centro de Astrobiologia, Universidad de Valladolid, 47006-Valladolid (Spain)
2Johannes Gutenberg-University Mainz; Institut fur Anorganische und Analytische Chemie AK KlingelhOfer Staudinger Weg 9
D-55128 Mainz Germany
Introduction: Although any place on Earth can be Experimental

precisely considered like Mars, study of places in Micro-Raman spectra were performed using a portable
which geological and mineralogical processes can be i-Raman spectrometer (B&W TEK) adapted to work at
used as potential Martian analogues is an important the field illuminated with a Ne-YAG laser at 532nm
step in developing the science and the instruments and with a power on the sample below 15 mW (spot
necessary for surface and subsurface analysis of the size of 1OO~m). The optical head was positioned in
red planet in the future missions. front of the samples using a mechanical device which
ExoMars is considered the first flagship mission of the allows mapping the surface at near the mineral grain
European Space Agency (ESA) within the long term scale. a power en the sample below 15 mW (spot size
program Aurora and in which a suite of dedicate in- of 1OO~m). The optical head was positioned in front of
struments will analyse the surface and subsurface of the samples using a mechanical device which allows
Mars up to 2mtrs depth with the main objective of mapping the surface at near the mineral grain scale.
searching for signs of past or present life. An impor- For in situ Mossbauer spectroscopy at Rio Tinto, two
tant part of this analysis is the precise characterisation MIMOSII sensorheads were equipped with "Co-
of the mineral phases produced by water-related proc~ sources (-30 mCi). The in situ power supply was en-
esses and in particular sulphates which have been re- sured by two car batteries. The data presented here
cently described on Mars [1-3]. show that spectra of good quality can be obtained
Among the techniques included in the ExoMars pay- within less than two hours and at temperatures of
load micro-Raman and Moessbauer spectroscopy will -35°C. The enhanced follow-up version of the spec-
play an important role in studying the Martian surface. trometer, MIMOS IIA for the ESA ExoMars mission,
Both instruments are linked to the rover's robotic ann will be equipped with silicon-drift-detectors (SDD)
and constitute the contact-analytical forefront for sur- instead of Si-PIN detectors, thus providing a signifi-
face mineral analysis of the mission. Their combined cantly better signal-te-noise ratio. The spot diameter
use in field campaigns is of great importance for defor a measurement is 15 mm.
veloping the science and the operation methodology
associated with the mission's objectives. Results Fig. 1 shows the combined operation ofRa-
Rio Tinto (Situated in the SW of Spain) is considered a man and Moessbauer at two places of Rio Tinto (Pefia
modem model of formation of sulfates, linked to del Hierro and the source of the river).
significant acidophilic biogenic activity. Sulfates
mainly come from aqueous alteration of iron-rich
sulfide minerals of the Iberian Pyrite Belt [4]. Rio
Tinto has been studied in recent years as potential
Martian analogue including micro-Raman analysis of
minerals and acidic waters [5-7] and combination of
Moessbauer and Raman [8] for mineral
characterization of evaporate samples taken at
different periods ofthe year. Nevertheless, no dedi-
cated in-situ analyses of the evaporate minerals of Rio Figure 1. Raman and Moessbauer spectrometers work-
Tinto have been performed at our knowledge using ing simultaneously at the Pena del Hierro, letf(mas-
combined techniques as micro-Raman and Moess- sive Fe-Oxides and hydroxides) and at the source of
bauer. It is the main aim of the present work to show the river, right (evaporate sulphate minerals).
the results obtained at the first field campaign per-
formed at Rio Tinto during the summer 2008. Three Figure 2 shows some of the Raman spectra obtained at
places were mainly studied paying special attention to the source of the river. This area constitutes the most
secondary minerals as the results of hydrological activ- recent evaporate mineral formation mediated by bacte-
ity in the area and the evaporate mineral as the direct rial activity. Copiapite is mainly detected as well as
product of the acidic water evaporation mediated by Epsomite which is in some case partially transformed
the acidophilic activity. in Hexahydrite. Jarosite and Gypsum was also detec-
ted. Figure 3 shows Mossbauer spectra obtained on

white/yellow evaporites (pure copiapite) and on white
crust ure melanterite).
__-.J
1>.lo·1ll
",·.f :::::=::::::::::==E~=-
'1J1o'Cll~
~ n @ " ~ • ~ rn ~ ,~ ~ ~ ~
-,.-'
Figure 4. Raman spectra obtained at El Huerto del
Loco area on white crust. A: Jarosite, B-D: Copiapite
with different hydratation, E: Coquimbite.
Figure 2. Raman spectra obtained in-situ at the Rio
Tinto source area. A: pure Copiapite, B: Epsomite, C:
Epsomite+Hexahydrite.
\.Hi
\.14
.,. ..,,-.
CQ()llIplte(29';b) _ _
.wosil.{71'll,) _
;' ~
1.12
.~
--= 1-
1.\
_.~ ._u . c..=' L"

1,~ f~1 •
8'''
Ij " 1
\
Ii '.'.
,I
I\
, \
,04
1.02
'010 rI
~1'I.
f1
,~.lU -'.
l' \
.'.2
,f·.,~-i/1'~
•. ~.'t.:tf'::-:.~ ~,.;;,;~.~'...!'~'
..... ,~*.-;4:;.\<?' ''''i;';''y,<~:';
-
-,-
0
-- .. .. ~ 0 • 0
Vtlooity(mrnIs)
2
Figure 3. M6ssbauer spectra obtained on white crust Figure 5. Mossbauer spectra obtained at EI Huerto
(left) and white/yellow evaporate (right). del Loco area on white crust (copiapiapite, possibly
with coquimbite) on top of red substrate (jarosite).
Figure 4 shows several Raman spectra obtained on
evaporate sulphates at the Huerto del Loco Area. At References: [1] KlingelhOfer, G., et al. (2004),
this area, it is possible to find rocks with secondary Science, 306. [2] Morris, R.V., et al. (2006b), JGR,
mineralogy and young (between 1500 and 2000 years lll, E12S15. [3] Squyres, S., et al. (2004), Science
old) terraces with mineralogical selection caused by 306. [4] D.Fernandez-Remolar et al. (2004) Planet.
the effect of physical transportation through the river. Space. Sci. 52, 239. [5] Amils R., et al. Planetary and
Copiapite and Coquimbite are the main mineral spe- Space Science, 2007. Vol. 55, Pag. 370. [6] Edwards
cies detected together with Jarosite. H.G.M., et al. Spectrochimica Acta Part A: Molecular
In the Mossbauer spectra obtained on these materials and Biomolecular Spectroscopy. 2007 Vol.68 pag.
(Figure 5), the substrate is visible through the rather 1133. [7] Sobron P. et al. (2008) Spectrochim. Acta A,
thin crusts. In addition to the signal from the crust it- 71,1678. [8] F. Rull et al. LPSC XXXIX·2008, 1616.
self (copiapiapite, possibly with coquimbite), a clear Acknowledgements: This work was supported by the
substrate signal Garosite) is visible in the Mossbauer Ministerio de Ciencia e Innovaci6n, Project ESP-
spectra. The different percentages of crust and sub- 2007-64998 and the CAB Research Program. We also
strate material in these spectra result from the crust acknowledge the support by the University Mainz and
thickness and Fe content of both crust and substrate. the German Space Agency DLR under contracts
Thus MIMOS II is able to measure a surface layer and 50QM9902, 50QX0603, and 50QX0802
the underlying substrate simultaneously, providing
depth-selective information. This combination of crust
and substrate could not be sampled for analysis in the
laboratory, demonstrating the value of in situ meas-
urements.
MINERAL CHARACTERIZATION OF SILICIFIED CORAL FROM WESTERN SUMATRA,

INDONESIA. L. Sanchez-Munoz!, M.A. Bustillo2, J. Garcia-Guinea2, E. Crespo-Feo 2, L. Tonno2; !CIEMAT. Av.
Complutense 22, Madrid 28040, Spain, correspondence: luis.sancheZ@ciemat.es. 2Museo Nac. Cien. Naturales,
CSIC, Jose Gutierrez Abascal 2, Madrid 28006, Spain.
Introduction: Coralline reefs fanned initially by

aragonite are particularly susceptible to diagenetic
modifications (calcitization, dolomitization and silici-
fication) because their high porosity, but the formation
of levels that can be useful as gemological materials is
rare [1,2]. Understanding of mechanism operating in
hydrothermal silicified fossil fonnation is particularly
important in the search of life beyond the Earth [3).
An interesting silicification process has occurred in
several localities in Barisan Mountains, Western Su-
matra (Indonesia) producing levels appropriated to
obtain gem materials. An exceptional sample (Mio-
cene?) was selected for this work because of its ex-
traordinary good structural preservation and beautiful
character. Sample (Fig. I) has been studied by optical
microscopy (OM), microprobe Raman spectroscopy
(MRS), and scanning electron microscopy (SEM) in-
cluding image fonnation by back scattered electrons
and chemical composition by energy dispersive X~ray
analysis (EDX), to correlate composition and crystal-
linity with fossil structures and to identify the origin of
the silica source.
Fig. 1. Silicified coral from Western Sumatra.
Experimental: The silicified coral was studied in a

polished section showing circular sections of the cor-
als. The SEM-EDX works were performed by using an
Inspect-S microscope from the FEI Company, without
carbon coating at atmospheric conditions. The MRS
study was perfonned by means of single spectra and Fig. 2. Hyperspectral Raman images of silicified
hyperspectral contour plots using a new Ther- coral showing: (a) contrast in low crystallinity regions.
moFischer Raman Microscope with one micron spatial b) Idem in high crystallinity regions. (c) Distribution
resolution and a laser source at 532 nm. of carbonaceous material mainly in septae and core
areas.
Results and Discussion: The silicified coral is mas· References: [I] Lund E.H. Am. Mineral., 45,
sive, dense without significant porosity because it was 1304-1307. [2] Tsintsov Z.L. et al. (2001) Neues Jahr.
almost totally replaced by SiO, minerals, and only Mineral. Mona/sh. 10,464-480. [3] Preston LJ. et al.
very residual areas have been found to be fonned by (2008) Icarus 198, 331-350. [4J G5tze et. al.(1998)
aragonite carbonate. Two different types of silica were Con/rib. Mineral. Pe/rol. 133, 96-105. [5] Nemanich
correlated with coral structures, from hyperspectral R.J. and Solin SA (1979) Phys. Rev. B, 20,392-401.
Raman 2D mapping (Fig. 2a and 2b). Radial (septae), [6] Jobson D.H. et al. (1994) 1. Geochem. Explora/ion
inner circular walls, and the core of the corals (yellow, 50,409-428.
green and blue areas in Fig.2a) are built up mainly of
silica with a very low crystallinity (opal), particularly
at the core (blue areas, Fig 2a). However, inner cav-
erns limited by previous elements are filled with
megaquartz crystals (red areas in Fig. 2b) and chalced-
ony fibres at the boundaries with the radial walls
(green areas in Fig.2b).
Micro-Raman spectra show that the inner parts of
the chambers are made of a-quartz (Fig 3a), character-
ized by peaks at 1160, 465, 204 and 127 cm· l that cor-
respond to region 1 in Fig. 4a and b. In chalcedony
areas (2 in Fig 4a and b), a broad band centred at circa
700 cm- l coexists with moganite (b in Fig. 3) with a
typical peak at 502 cm- l [4). 0 signal at 465 cm· l can
be recorded in opal regions (3 in Fig. 4), but carbona-
ceous matter was detected by Raman spectra [5], in
small grains as seen in Fig. 2c.
Quartz 465
204
1160
Moganile ~
502
G band D band
1580 1331
• Ii, •• Ii. iii'

1500 1000 500
Raman shift (em- 1)
Fig. 3. Raman spectra of a) a-quartz, b) chalcedony,
with moganite, and c) opal with carbonaceous matter.
The source of silica is difficult to establish but the

presence of AgS (and also Zn-Cu) minerals linked to
fractures inside the silicified coral (Fig. 4c) indicate a
hydrothermal origin. Low-sulphidation epithermal Ag Fig. 4. Textures: (1) Opal, (2) chalcedony, and (3)
deposits are well being exploited in Barisan Mountains megaqua~ in silicified coral observed by optical mi-
(Sumatra) with the mineralization in the form of croscopy using parallel (a) and crossed nicols (b).
quartz-cemented breccias [6]. Then, the coral silicifi- c) BSE image and EDX spectra of Ag-rich particles.
cation resulted from interactions with hydrothermal
water having a high amount of dissolved silica derived Acknowledgements. Supported by the project CGL-
from local volcanic activity. 20008-05584-C02-01 and aJAE-Doc CSIC contract.
CATHODOLUMINESCENCE (CL) STUDIES OF UHP·METAMORPHIC ROCKS FROM DORA

MAIRAIWESTERN ALPS: PETROLOGICAL APPLICATIONS AND HIGH RESOLUTION
SPECTROSCOPY. H. P. Schert! , T. Gotte, R. D. Neuser and D. K. Richter, Ruhr-Universtat-Bochum, Instimt fUr
Geologie, Mineralogie und Geophysik, Universitatsstr. 150,44801 Bochum, Mail: hans-peter.schert!@rub.de
The UHP-metamorphic rocks from the Dora Maira rock-forming minerals document an invaluable impact
Massif (Northern italy) are an ideal candidate to demon a more precise derivation of PT-paths and thus on
onstrate the great advantage of a hot CL-microscope the evolution of geodynamic processes with any
[1], in particular if it is used in conjunction with elec- metamorphic rocks involved. Thus, we propose that
tronmicroprobe (EMP) and high resolution spectros- the CL technique should be used more intensely for
copy measurements. The compilation of data shows routine investigations of thin sections of metamorphic
oscillatory zoning patterns of garnet (reddish brown to rocks as a pathfinder prior to chemical characterization
bluish luminescence) and the change of its morphology by EMP.
during growth. Typically garnet shows an increase of
brightness from core to rim with an outermost late gar- a. kyan~e, blue
net generation lacking luminescence. CL also reveals a
zoning of kyanite (blue, red) probably indicating two
kyanite-forming reactions. Different crystallographical
orientations of twinned kyanite result in various lumi-
nescence colours. Jadeite crystals (yellow, green)
partly show a very irregular zonation. Si02-phases as
well as e.g. distinct generations of quartz are easy to
disinguish since they display characteristic CL colours
(coesite: bluish green, quartz: dark red to violet, chal- b. pyrope. red
cedony: yellow). Additionally special features of fur-
ther minerals like zircon, apatite, bearthite, phengite
are discussed. I
Using high resolution spectroscopy of CL emission
(HRS-CL) [2], kyanite, pyrope and jadeite show char-
acteristic spectra:
kyanile - blue = intrinsic CL with a broad band at 500

nm and narrow bands of Cr'+ at 688.5 nm and 705.2 c. jadeite, yellow
nm superimposed by a broad band at 710 nm (see Fig.
a).
kyanile - red = narrow bands of Cr'+ at 688.5 nm and
705.2 nm superimposed by a broad band at 710.
pyrope - ochre = D/+-, Sm3+_ (and Th3+_) narrow
bands.
pyrope - dark grey-ochre = narrow bands as above,
but lower intensity (higher Fe·content according to
-
EMP).
pyrope - brown = narrow bands as above and weak. References:
broad band at 690 nm. [lJ Schertl, H.-P., Neuser, RD., Sobolev, N.V. and
pyrope - red·brown = narrow bands as above and Shatsky, V.S. (2004): UHP-metarnorphic rocks from
strong broad band at 690 nm (see Fig. b). Dora MairaIWestern Alps and KokchetavlKazakhstan:
jadeile - brighl yellow green ~ Mn'+ broad band at 560 New insights using cathodoluminescence petrography.-
run (see Fig. c). Eur. J. Min., 16: 49 - 57.
jadeite - green = Mn 2+broad band at 563 nm. [2] Habermann, D., Neuser, R.D. and Richter,
D.K. (1996): REE-activated cathodoluminescence of
Although being mainly descriptive, the conclusions calcite and dolomite: High Resolution Spectrometric
drawn open new avenues for petrological applications. analysis of CL emission (HRS-CL). - Sed. Geol., 101:
Our studies on detailed structural characteristics of 1-7.
UNCOMMON CALCITE CRYSTALS IN CAMBRIAN AND ORDOVICIAN LIMESTONES FROM

ONSHORE AND OFFSHORE NORTHERN POLAND - EVIDENCE FROM CATHODOLUMINESCENCE
Magdalena Sikorska, PaI\stwowy Instylut Oeologiczny, ul. Rakowiecka 4, 00-975 Warszawa; magdale-
na.sikorska@pgi.gov.pl
In the Cambrian of the Polish sector of the Baltic single ooid grains and excellently developed zoned
Depression, limestone occurrences are known only structure of the feather-like calcite crystals.
from the uppermost portion of the section. The Upper
Cambrian deposits are represented by black bituminous
claystones with thin limestone interbeds and lenses.
They were deposited in a euxinic marine basin proba-
bly on a carbonate ramp. The lowermost Ordovician
(Tremadocian) section is a continuation of the Late
Cambrian sedimentation of the black bituminous shales
with graptolites which are overlain by glauconite con-
glomerates, claystones and limestones. Carbonates are
dominant in the Arenig and Llanvirn, whereas upper in
the section they are represented by interbeds within a
claystone succession (Modlinski et aI., 1994). The in-
vestigations were carried out on Limestone samples ="..]
from wells drilled both offshore and onshore in the Fig.2. Calcite pseudomorphs (c) after sulphates in
Baltic Depression. limestone with calcite crystals showing zoned structure
The Cambrian limestones are represented mostly by visible in CL. a) TrL image - plane-polarized light; b)
biosparites containing variable amounts of faunal CL image - the same object as in a. Upper Cambrian,
fragments, organic matter, pyrite, phosphates and detri- Zamowiec [04 borehole, depth 2708.0 m.
tal grains. The rocks are strongly recrystallized and
their original structure has been significantly blurred. Central parts of the crystals are automorphic (hex-
Microscope images reveal that some parts of the rocks agonal) grains overgrown by a succession of zones
(microlenses) consist of elongated calcite crystals, showing different luminescence patterns. Their outer
sometimes of feather-like structure, accompanied by parts are commonly less regular, bearing signs of disso-
abundant organic matter (Fig. Ia). lution (see Chafetz et aI., 1985; Rossi & Canaveras,
1999). The pore space between the crystals is filled
with abundant organic matter. It seems that these un-
common calcite forms resulted from specific conditions
in rnicroareas where organic matter accumulated due to
the dying of organisms and soft tissue decaying. The
calcite crystals had enough space to easily crystallize.
This interpretation is especially likely if there was co-
occurrence of calcite pseudomorphs after sulphates
(Bodzioch, 2005), whose presence was proved by CL
images. Sulphate crystallization (barite / celestine) was
associated with a process of soft tissue decay, supply-
ing sulphur to the environment (Fig. 2). The Ordovi-
cian carbonates are represented mainly by biomicritic
Fig.I. Calcite crystals with zoned structure visible in and biomicrosparitic limestones. Calcite crystals which
CL. Pore space between the crystals is filled with or- are similar to those from the Upper Cambrian deposits,
ganic maner (black colour). a) TrL image - plane- in the Ordovician limestones are less conunon.
polarized light; b) CL image ~ the same object as in a. Carbon and oxygen isotope composition analyses of
Upper Cambrian, BI6-1/85 borehole, depth 1860.4 m. the Upper Cambrian limestones indicate that the aver-
age value of O"C rDB is -2.30%0 (ranging from 0.43 to -
Cathodoluminescence studies (CL) revealed the 6.89%0), whereas the average value of Ol80PDB is -
original structure of the limestones (Fig. lb). CL im- 8.06%0 (between -6.67 and -8.83%0). The study results
ages clearly show the occurrence of organic fragments, suggest that the primary rocks were limestones which,
74 LP1 Contribution No. 1473
although Cambrian in age, have not significantly

changed their isotopic composition of carbon. That
was possible because the limestones occur as isolated
bodies within the bituminous claystone facies. The
temperatures at which the limestones formed (calcu-
lated from the 15 18 0 values, assuming that 15 18 0 for sea
water ranges from -6 to -70/00 SMOW) varied between
24.8'C and 19.6'C.
Isotopic composition of the Ordovician limestones
is similar, although shifted towards higher values of
1513 CPDB and 15180 PDB ' The average value of 1513 CPDB is
0.26%0 (from 3.64 to -5.10%0), whereas the average
li"OPOB is -6.91%0 (from -3.67 to -12.69%0). Assuming
that 15 18 0 for sea water in the Ordovician was between-
5%0 and -6%0 SMOW, the temperatures at which the lime-
stones formed varied from 24.0°C to 19AOC.
REFERENCES
[I] Bodzioch A. (2005) Biogeochemiczna diageneza
dolnego wapienia muszlowego Opolszczyzny. Uniw.
1m. A. Mickiewicza w Poznaniu, Seria Geologia 17.
Wyd. Nauk. UAM
[2] Chafetz H.S., Wilkinson B.H. & Love K.M. (1985)
Morphology and composition of non-marine carbonate
cements in near-surface settings. In: Carbonate ce-
ments (eds. N. Schneidermann and P. Harris). SEPM
Sp. Publ. 36.
[3] Modlinski Z., Nehring-Lefeld & Ryba J. (1994)
The Early Palaeozoic Complex in the Polish Part of the
Baltic Sea. Z. geol. Wiss., 22 (112), 227-234.
[4] Rossi C. & Canaveras J.c. (1999) Pseudospheru-
litic fibrous calcite in Paleo-groundwater, unconfonn-
ity-related diagenetic carbonates (Paleocene of the
Ager Basin and the Miocene of the Madrid Basin,
Spain). J.Sed. Res. Sec. A. 69, 224-238.
ORDER-DISORDER IN K-FELDSPAR GROWN FROM MIXED MAGMAS - CL AND RAMAN STUDY. E.Slabyl,
lGotze2 , G.Worner3, K.Simon 3, R.Wrzalik 4 M.Smigie1skis, 1Institute of Geochemistry, Mineralogy and Petrology, University of
Warsaw, 02-089 Warsaw, AI. Zwirki 1 Wigury 93, Poland, e.slaby@uw.edu.pl. 2Institute of Mineralogy, TV Bergakademie
Freiberg, Brennhausgasse 14, D-09596 Freiberg, Gennany, 3Departrnent of Geochemistry, GZG of Georg-August-University,
37077 Gottingen. Goldschmidrstrasse I, Germany, 4Institute of Physics, University ofSilesia, 40-007 Katowice, Uniwersytecka
4, Poland, 5 Institute of Geology, University of Warsaw, 02-089 Warsaw, AI. ZWirki i Wigury 93. Poland.
Introduction: The description of the pattern of or- tra collected within barium-rich zones show doublet
der-disorder in K-feldspars is complicated because of pattern and those collected from barium poor zones
numerous modes in which Al and Si can be distributed present triplet patterns. In the patchy rones light blue
among T sites (substitutional disorder) and because of domains with doublet Raman pattern are adjacent to
their (Si, AI) charge linkage to M atoms. This pattern dark blue displaying triplet pattern in the 450-512
we investigated in K-feldspars crystallized from stirred cm-I wave-number range.
coeval magmas of contrasting thennal conditions and Relation between magma~, crystal·composition
contrasting geochemical composition. and crystal.order-disorder pattern: Trace element
The feldspars have been collected from different, patterns of K-feldspar points to chemical mixing of
early and late, mixing events occurring during a pluton contrasting magmas. Mixing was incomplete and that
fonnation [1]. The study had been perfonned using is why several domains preserved signals from almost
mainly LA ICP MS, CL and Micro-Raman Spectros- pure end-member magma compositions. During
copy [2]. The investigated K-feldspars show ronal magma mixing chemical exchange is preceded by heat
growth, which reflects lack of perfect homogenization exchange, which usually goes to full completion very
of both mixed magmas. Zonal growth texture is visible fast. That is why we believe, that the thennal gradient
under CL, due to different structural defect density e.g. cannot significantly influence substitutional disorder in
order-disorder within zones. investigated feldspars. The order-disorder is caused by
It is well known, that "with falling temperature M-T linkage and is influenced by local magma compo-
substitutional disorder becomes less stable and a feld- sition. The wnaVdomain partern (geochemical and
spar solid solution proceeds to ordered structure" [3]. structural) revealed by both CL and Raman study can
The aim of the study was to prove, whether differences be related to the dynamic of mixed magmas and the
in order-disorder revealed by CL in individual zones degree of their homogenization.
can be related to thennal gradient in both mixed mag-
mas or should be related to other factors.
CL data: The crystals show more or less concen-
tric zoning. Some of the zones are patchy. They differ
in intensity of bluish color activated by varying densi-
ties of AI-O--A1 structural defects (-450 nm CL
emission [4]) and by differing concentrations of Fe3+
•
activators (-700 nm CL emission; [5]). Light blue
color, which is caused by high density of structural
defects appears in zones highly enriched in barium as
well as Sf and LREE. Dark blue color becomes visible CL Intensity (counts)
in zones impoverished in all mentioned above these
elements. Barium substitution causes local structural
Fig.l Correlation between Ba content in feldspars
distortion due to coupled KSi-BaAl exchange. In addi-
(taken from samples presenting early, middle and late-
tion FeJ + (or similar cations)-AI J + substitution can also
stage of hybridization) and density of AI-o--AI de-
rearrange the distribution of AI in tetrahedral sites.
fects (intensity of -450 nm peak)
Micro-Raman data: Assuming that trace element
incorporation is responsible for the formation of AI-
Usu.ally, mixing proceeds through many events.
O--AI centers e.g. changeable order-disorder, one
Feldspars collected from early, middle and late event
should collect different Raman spectra within individ- show the same characteristics with similar growth,
ual zones/domains. Transition of disordered to ordered
trace element, CL and Raman spectra pattern based on
structure is matched in Raman's spectra by change of structural defect densities. The density of AI-o--AI
doublet into triplet pattern in the 450-512 cm- 1
defects is enhanced during growth in mixed magmas
(bending vibration mode) region [6]. Indeed the spec-
76 LPJ Contribution No. 1473
and changes when we compare early and late events of

mixing (Fig. I). The density of defects progressively
diminishes in feldspars crystallized in late hybrids.
Mixing occurred while magmas were in the process
of differentiation. Therefore, magmas became progres-
sively enriched in fluids. Late events of mixing oc-
cured between two most evolved and fluid rich mag-
mas [1]. Feldspar is fluid absent phase, but fluids
stimulate ordering process of its structure. The inten-
sity of AI-O--AI related CL emission shows, that the
density of structure distortion decreases markedly in
growth zones that fanned during late mixing events.
We believe that decreasing intensity of AI-{)--AI
related CL emissions in feldspars which formed at the
last stages of magma interaction reflects two contrast-
ing effects: of magma composition stimulating appear-
ance of structure distortions and fluid influence reduc-
ing progressively these defects density.
References:
[I] Slaby E. and Martin H. (2008) JP, 49, 353-391.
[2] Slaby E. et al. (2008) Lithos, 105,85-97. [3] Smith
J. and Brown W. (1988) Springer. [4] Marfunin A.S.
and Bershov L.V. (1970) Doklady Akademii Nauk 193,
412-414. [5] Gtilze J. et al. (2000) Springer. [6] von
Stengel M.a. (1977) Zeitschrif/ fiir Krystalographie
146,1-18.
Additional Information: The work has been
founded by grants: BW 1642, BST 1241/8 and
NN307176633.
Conference On Micro-Raman Spectroscopy and Luminescence Studies 77
RAMAN SPECTROSCOPY, A POWERFUL TOOL FOR THE CHARACTERIZATION OF HYDRATED

SULFATES AND ACIDIC WATER IN RIO TINTO (SPAIN) P. Sobron, A. Sansano, A. Sanz, T. Acosta, B.
Lafuente, F. Rull, F. Sobron, J. Medina, Unidad Asociada Universidad de Valladolid-CSIC a traves del Centro de
Astrobiologia. Paso Prado de Magdalena sin. 47011 Valladolid, Spain (psobron@iq.uva.es)
Introduction: The discovery of ferric hydrox- been derived from the Raman spectra of stream waters.
idesloxyhydroxides, jarosites (iron-bearing sulfates The in-situ Raman spectroscopy of the acidic stream
thought to have fonned via aqueous activity) and other waters and related mineralogy is also reported.
sulfate-bearing minerals in the Meridiani region pro- Experimental:
vides strong evidence that liquid water once flowed on Samples:
the Martian surface [1-4]. It is suggested that sulfate Efflorescent salts from acidic surface stream wa-
deposits enriched in iron and mixed iron oxy- ters were collected from several sampling spots near
hydroxide were precipitated from meltwaters, thought the site considered as the source of the river, Pefia de
to have been acidic yet hydrothennalism and volcan- Hierro (Spanish for iron mountain). Water samples
ism could have played a role shaping the Meridiani display yellowish-to-reddish colors whereas solid sam-
surface conditions as well. Terrestrial acidic and sul- ples show while, yellow, orange and dark red colors as
fate-rich sites such as Rio Tinto and EJ Jaroso in Spain, shown in Fig. 1.
Iron Mountain in California, and some lakes in West- Raman instrumentation:
ern Australia are exceptional sites for the study of acid- Raman spectra of the aqueous samples were col-
ic waters, its associated precipitates and efflorescent lected in the laboratory at a constant temperature of 20
salts, and sulfate-fonning processes in general. The °C with a con-focal Raman microscope (WiTec al-
characterization of the hydrogeochemistry of these pha300 R) in the spectral range 75-3900 cm·'. The
sites is crucial in order to describe all of the different spectral resolution was I cm· l . The 532.4 nm line of a
processes and settings of iron and sulfate deposition on frequency doubled Nd:YAG laser was used as excita-
Earth. As these localities host mineralogical signals tion source. Solid samples were placed on a 3D-motion
detected on Meridiani, the comparison may help to stage of a Nikon Eclipse microscope, equipped with
understand how the Meridiani minerals fanned. 5 x , 20x and SOx objective lenses. The microscope is
Raman spectroscopy is regarded as a powerful cha- connected to a Kaiser HoloSpec lll.8i spectrograph. A
racterization technique for the sulfate systems due to CCD attached to the spectrograph was used to collect
its intrinsic features: it requires little or no sample the Raman spectra. The 632.8 nm line from a He-Ne
preparation prior to spectra collection, and allows real- laser was used excitation source. The spectra were
time identification of species in acidic waters and as- recorded within the region 200-3800 cm- I with a spec-
sociated precipitates and very rapid quantification of tral resolution of 4 em-I. In the field, Raman spectra
their abundance, among others. Furthermore, recent were recorded. without any sample preparation, using a
advances in optics, lasers and detector systems allow field portable B&W Tek i-Raman spectrometer
for the development of compact field Raman instru- equipped with a laser at 532 nm.
ments for in-situ analyses. This fact, together with the
capabilities of the Raman spectroscopy for the unam-
biguous characterization of mineral phases and poten-
tial biosignatures, make the Raman technique an out-
standing tool for the exploration of sulfate-rich areas,
and most likely for the Martian surface and subsurface.
A landmark for the technique is the selection of a con-
contact combined Raman-LIBS spectrometer as a fun-
damental instrument within the upcoming European
Space Agency (ESA) ExoMars mission (2016).
In this work we report the Raman spectroscopy of
some aqueous solutions and associated precipitates
(found in coexistence in most cases) of Rio Tinto (SW
Spain). Spectral fingerprints from various fonns of
iron sulfates have been found in the minerals and as
such are used for their identification. The relative ab-
undances of sulfate and bisulfate ions and water have Fig. 1
Results: The laboratory Raman spectra of both wa- knowledged for her assistance with the Raman analysis
ter and solid samples are plotted in Fig. 2. Variable at the University of Hawaii at Manoa, The Ministery of
amounts of sulfate and bisulfate are found in the aque- Science and Innovation (project ESP-2007-64998),
ous samples, suggesting changes in the acidity of the through a grant to Center of Astrobiology (Madrid,
solutions. The sulfate/water relative abundance has Spain) made the field trip to Rio possible. The Univer-
been estimated from the derived relative intensities of sity of Valladolid is also acknowledged.
the associated bands: 982, 1044 and 1640 em" for sul-
fate, bisulfate and water, respectively (Table I). Solid
1
samples are identified as gypsum and as mixtures of
hydrated iron(JI)/iron(lII) oxides belonging to the I
copiapite-group and jarosite-group.
Fig. 3 shows some of the Raman spectra collected
1 4 ~I
at the Rio Tinto source (solid lines). The spectra have
been offset for clarity and some spectra from reference
materials have been overlaid for comparison purposes
(dashed lines). The spectrum RTNcsOl, showing two
pairs of intense bands at approximately 995/1108 cm"
and 102111132 cm", is consistent with the presence of
copiapite in the sample. The spectra RTNcs02 and 03
do not show the two pairs. It is well known that the v,
symmetric stretching band of sulphate ion (around 982
cm'l) in ferrous iron shifts with hydration state of the .., ." .1110 ':l!lII Ie) ._ '101 'Pil _ tOOO _1100 T2llO l300
_ 10'1"
salt. The presence of three and two bands in the spectra _ _ICIlIO'
RTNcs02 and 03 in the 970-1020 cm" region, respec- Fig. 2

tively, may be indicative of a mixture of hydrated
iron(II) sulfates, likely following a sequence of dehy-
dration from the evaporated salt. Whereas spectrum
RTNcs02 shows fingerprints of melanterite
(FeS04'7H20), rozenite (FeS04'4H20) and sromol-
Fig. 3 --
--
nokite (FeS04'H20), only the two latter are present in
1_ ~==--
spectrum RTNcs03. The spectrum RTNcs04 shows a
single band centered approximately at 983 cm" . Rather
1 A
,~~~~;.J.~:p§.'.~~. ~~::~.:::::~:::::::§:~g
than iron sulfate, the position of this band is more con-
sistent with the presence magnesium sulfate in the
sample, most likely epsomite.
Conclusion: Off-site and on-site Raman spectros- n. uo 000 ,.,
copy has been used as a means of characterizing the ftom,n"'rII«,.,·I!
hydrogeochemistry of Rio Tinto area. Variable
amounts of sulfate and bisulfate ions have been meas-
ured in the streams waters close to the source of the Table 1
river, Gypsum and ferrous and ferric sulfates have Band relative intensity
been detected in the efflorescences. A portable Raman , ,
spectrometer has been used for in-situ analysis of Rio
Tinto stream waters and mineralogy thus justify the
Sample
RTN(Ob
982 em 1044 em
. ..
1640 em •
..
importance of Raman spectroscopy as a potential tool
for the characterization of Rio Tinto hydrogeochemis-
RTNCO
RTNRN
'.
,.
,.
• ..
try and hence of any environment relevant for plane-
tary exploration.
RTNRE
RTNRO .
References: [I] Klingelhofer et al. (2004) Science,
306, 1740. [2] Clark et al. (2005) Earth Planet. Sci.
Lett., 240, 73. [3] Rieder R et al. (2004) Science, 306,
1746. [4] Lane et al. (2004) Geophys. Res. Lett, 31,
L19702, doi: 10.1 02912004GL02l231
Acknowledgment: This work has been supported
in part by the Re-search Council of Spain (CSIC)
through grant no. UAC2005-007. Lydie Bonal is ac-
IDENTIFICATION OF MINERALS IN DAG 610 AND IN NWA 869 METEORITES BY MICRO-RAMAN

SPECTROSCOPY. M. Szurgoe, A. Karczemska 2, M. Kozanecki 3, T. Jakubowski 4, S. Mitura4, lTechnical Univer-
sity of Lodz, Center of Mathematics and Physics, AI. Politechniki II, Lodz, Poland, (mszurgot@p.lodz.pl),
2Technical University of Lodz, Institute of Turbomachinery, Wolczanska 219/223, Lodz, Poland, 3Technical Uni-
versity of Lodz, Department of Molecular Physics, Zeromskiego 116, Lodz, Poland, 4Technical University ofLodz,
Institute of Materials Science and Engineering, Stefanowskiego 1/15, Lodz, Poland.
Introduction: Ordinary chondrites DaG 610 (H4, Results: Figures I and 2 show optical images of
found in 1998) [I], and NWA 869 (L4-6, S3, WI; the meteorites. The presence of chondrules, matrix and
found in 2001 [2]) are new, interesting extraterrestrial kamacite patches in DaG 610 and in NWA 869 chon-
materials. Our previous investigations of DaG 610, drites, and of clasts in NWA 869 can be seen. Chon-
NWA 869 and Morasko meteorites by Raman spec- drules and the matrix consist of different minerals
troscopy were focused on revealing various carbon (Figs. 1 and 2).
phases [3]. Graphite was found in both these mete- Figures 3 and 4 present Raman spectra from vari-
orites, and lonsdaleite only in DaG 610 [3]. The aim of ous parts of the chondrites: from chondrules, from
the paper was to identify various, mainly silicate min- matrix, and from clasts. Various extraterrestrial min-
erals in NWA 869, and DaG 610 chondrites using mi- erals have been identified in the NWA 869 and in DaG
cro-Raman spectroscopy. 610 meteorites: olivines (Figs. 3 and 4), orthopyrox-
Experimental: We have examined one plate of enes (Figs. 3), clinopyroxenes (Fig. 4), feldspars (Fig.
DaG 610 meteorite (Fig. I), and one plate of NWA 4), graphite, and troilite. The presence of diamonds in
869 meteorite (Fig. 2). Raman spectra were done on DaG 610 has been established in our previous study
confocal Raman micro-spectrometer T-64000 (Jobin- [3].
Yvon) equipped with the BX-40 microscope (Olym-
pus). To excite the sample minerals Ar laser was ap-
plied (514.5 nm Ar line, the beam diameter about 1 OL
/lID), and acquisition time and laser power were ad-
Opx i!~
justed to obtain spectra of sufficient quality.
•
ii
/(; .>\\\\ 1200

Fig. 1 Photograph of the DaG 610 meteorite.
Raman shift (cm·1)
Fig. 3 Raman spectra of olivines (OL) and pyrox-

enes (Opx) from the chondrules of DaG 610. 824 and
j
856 cm- are DB 1 and DB2 dominant lines of the oli-
vine (Fa,Fo97 ). 342,663,682 and 1010 cm- l are do-
minant lines of the orthopyroxene (En97Fs3)'
\
Fig. 2 Photograph of the NWA 869 meteorite
sample showing chondrules and matrix of the mete-
orite. Various minerals, mainly pyroxene (OPX, red),
kamacite (blue), and olivine (green) can be seen.
Fig. 4. Raman spectra of minerals present in

NWA 869 meteorite. 324, 389, 665 and 1011 cm· 1
peaks in the upper spectrum reveal clinopyroxene
(Cpx) called pigeonite (ratio Mg/Mg+Fe+Ca~0.45).
The lower spectrum is typical of olivine (OL) (822 and
853 cm·! are OBI and DB2 peaks of olivine Fal7Fon.
478 and 515 cm-\ peaks seen in the upper spectrum
reveal feldspar, probably orthoclase.
Conclusion: The main chondrite minerals have

been identified in the NWA 869 and DaG 610 mete-
orites by micro-Raman spectroscopy. Most of them
are the same minerals that we have identified by ana-
lytical electron microscopy and optical microscopy in
thin sections.
References: [I) Grady M., Calaloglle of Mete-

orites, 5" ed., (2000), Cambridge Univ. Press, Cam-
bridge. [2) Conolly H.C. et aI., (2006), Meteoritics &
Planel. Sci., 41. 1383-1418. [3) Karczemska A. et aI.
(2007) Diam. ReI Mater., 16,781-783.
MICRO-RAMAN SPECTROSCOPY OF NWA 4047 METEORITE. M. Szurgot', K. Kisiel', and R. Kisiel',

ITechnical University of Lodz, Center of Mathematics and Physics, AI. Politechniki 11, Lodz, Poland, (mszur-
got@p.lodz.pl), 'Technical University of Lodz, Department of Molecular Physics, Zeromskiego 116, Lodz, Poland.
Introduction: NWA 4047 meteorite is a new 4047 meteorite: olivines (Figs. 4 and 6), orthopyrox-
extraterrestrial material that has been found in 2005 enes (Figs. 5 and 7), clinopyroxenes (Fig. 6), plagioc-
and classified as H4-5 ordinary chondrite [I]. Chem- lase (Figs. 6 and 7), graphite (Fig. 6). The presence of
ical and mineral composition of the meteorite, petro- diamonds is possible but it must to be verified.
logic types of chondrules, their abundance and sizes
have been studied by electron and optical microscopy
[2J. The aim of the paper was to identifY and character-
ize of minerals of NWA 4047 chondrite with micro-
Raman spectroscopy.
Experiments: We have examined one thin plate
of the meteorite, with the area of 25x25 mm 2 (Figs.
1and 2). Raman spectra were done on confocal Raman
micro-spectrometer T-64000 (Jobin-Yvon) equipped
with the BX-40 microscope (Olympus). To excite the
sample minerals Ar laser was applied (514.5 nm Ar
line, the beam diameter about 1 tLm), and acquisition
time and laser power were adjusted to obtain spectra of
sufficient quality, as in previous our studies [3,4],
Fig. 2 The thin plate of NWA 4047 meteorite.
Fig. I Photograph ofNWA 4047 meteorite.
Results: Figures 1 and 2 show optical images and

Fig. 3 SEM X-ray cameo image of the NWA 4047
figure 3 X-ray Cameo image of the NWA meteorite.
sample showing chondrules and matrix of the mete-
The presence of chondrules of diffenet sizes and vari-
ous minerals in chondrules and in the matrix can be orite. Various minerals, mainly pyroxene (OPX, red),
kamacite (blue), and olivine (green) can be seen.
seen. The existence of some number of clasts can also
be also noted.
Figures 4, 5, 6 and 7 present Raman spectra from Conclusion: The main chondrite minerals have
various parts of NWA 4047 meteorite: from chon- been identified in the NWA 4047 meteorite by micro-
drules, from matrix, and from clasts. Various extrater- Raman spectroscopy. Most of them are the same min-
erals that we have identified by analytical electron
restrial minerals have been identified in the NWA
microscopy and optical microscopy [2].
9000,--------------, 5000 , - - - - - - - - - - - - - ,
8000 PI.
7000
6000
5000 ~ i
:: I ~
2000 ' : \.! ~ I
10~ t::::::~:::=::::::.-~:~-:::...,::'
300 500 700 900 1100
Rlman shift [cm·1l
Raman shift [em-')
Fig. 4 Raman spectrum of olivine (OL) from the

Fig. 7 Raman spectrum of plagioclase (PL) present
ehondrule. 823 and 854 em" are DBI and DB2 domi-
in the clast region of the NWA 4047 meteorite.
nant lines of the olivine (FanFo87).
Acknowledgements: The authors are grateful to
8000
7000 0" Dr Marcin Kozanecki, Dr Krzysztof Polanski and to
8000 Op, Op, mgr Marcin Krystek for the discussion of the results.
'"..'"c
.
5000
4000 References: [1) Conolly H.C. et aJ. (2006) Meleo·
:s 3000
2000
1000
L ~~ A L..
rilics & Planet Sci, 41, 1383. [2] Szurgot M. el aJ.
(2008) Crysl. Res. Technol., 43, 656-665. [3) Kare-
zemska A. et aJ. (2008) Diam. Rei Maler., 17, 1179-
300 500 700 900 1100 1300 1185. [4) Guesik A. et aJ. (2008) Proc. IAU, 4. 335·
Raman shifl [cm.il 340.
Fig. 5 Raman spectrum of orthopyroxene (Opx)
present in the matrix of the meteorite. Dominant lines
339,661,681 and 1010 em", MglMg+FetCa~0.82.
""" Cp' Cp'

350Il OL
Gr
3000
~
0 2500
c~
:5 2000
1500
1000
300 500 700 900 1100 1300 1500 1700
Raman shift [cm-1]
Fig. 6 Raman spectrum of minerals coexistent in
the matrix micro-region. Cpx - clinopyroxene (328,
366,393,669 and 1019 em" peaks, EJ4,Fs,Wo,,), OL-
olivine (822 and 853 em" are DB 1 and DB2 peaks),
Gr - graphite (1471 and 1610 em" peaks), and PL -
plagioclase (481 and 512 em" peaks) .
COMPARATIVE RAMAN STUDY OF DIFFERENT MARS ANALOG MATERIALS. 1 • Tarcea\ M. Hil-

chenbach', W. Goetz', H. Steinioger' and 1. Pappi.', I Institute of Physical Chemistry, University ofJena, Helm-
holzweg 4, Jena (Germany), 'Max Planck Institute for Solar System Research, Max-Planck-Str. 2, Katlenburg-
Lindau (Germany), email: hilchenbach@mps.mpg.de. 'Institute ofPhOlonic Technology, Albert-Einstein-StraBe 9,
Jena (Germany), Tel. +49 3641206300, email: juergen.popp@ipht-jena.de
Introduction: One of the next missions to Mars Raman spectra were measured at different laser ex-
(2016) is the European ExoMars mission which has citation wavelengths (476, 532, 568, 676 nm) with a
the declared scientific objectives, in order of priority: LabRam HR 800 spectrometer from Jobin Yvon. Ran-
• search for signs of past and present life dom measurements were performed with a microscope
• characterize the water/geochemical environment as on the powder samples.
a function of depth in the shallow sub-surface
• study the surface environment and identify hazards
to future human missions
• investigate the planet's subsurface and deep inte-
rior to better understand the evolution and habita-
bility of Mars.
As part of the scientific payload a Raman device is
currently under development. The objectives of the
Raman experiment are the detennination of the geo-
logical context at the rover sites with identifying rock-
forming. hydrated and water-related, altered and non- WO \000 lWO 2000 2~ :lOOO 3S00
altered mineral phases in exposed outcrops, rocks, and Relative Wavel"lymbers (~m-')
soils. The 'exobiology' part of the experiment aims at

identifying possible biomediated minerals, such as
Fig. 1 - Gedrite spectrum measured on the Riverside
carbonates as well as search for surface signs of past
sample with 532 om laser excitation.
life at the rover sites, e.g., through the identification of
certain pigments and organic molecules that can be
Identification of the organic molecules present into
associated with biology.
the samples was done using a gas chromatograph cou-
Laboratory experiments are performed trying to
pled to a mass spectrometer (GC-MS). A large variety
fully characterize different mineralogy models (mag-
of organic material have been found although in small
matic, water alteration, precipitation --evaporation)
concentrations (e.g. Benzol, Benwfuran, Toluol, Sty-
which are of interest for Mars. One approach is to use
rene, Naphtalin in JSC-I sample, Benwl, Pyrrol,
materials deemed as Mars analogues. This work aims Ethylcyclopenen, Ethylbenwl, Toluol, Styrol, Fural-
. at characterizing the aforementioned Mars analogues dehyd, Beznofuran, Phenol, [nden, Benwnitril, Naph-
using Raman spectroscopy which is a prerequisite step talin, Methylnaphtalin in Salten Forest material, Ben-
for further using the materials on subsequent Raman wi, Toluol, etc in Panther Creek Mars analogue).
experiments. Additionally, the small concentration of
organic materials present in these samples although not
directly measurable by the Raman experiment was
taken into consideration and their influence on the
recorded Raman spectra is discussed.
Experimental: The five different materials known
as Mars analogues used for this comparative study are:
(I) Mars analogue JSC-l
(2) Riverside, original batch
(3) Martian analogue Salten Forest
(4) Panther Creek, Colorado, US Wards 46E0435 +
46E0438
(5) Atacama sand Relative Wavel"lumbefS (crrfi
All of the samples were in a powder form with the Fig. 2 - Cechite spectrum measured on the Riverside
particle sizes under 50Jlm. sample with 532 nm laser excitation.
rendered most of the spectra useles-s. Nevertheless it

was observed that as soon as the incident laser power
is reduced at levels under 100 Jl W (laser diameter spot
on the sample was -2Jlm) the fluorescence back-
ground dropped drastically. A detailed discussion on
possible causes and the implication for in-situ Mars
Raman experiments is presented.
SOO 100(1 1SOO 2000 2500 XIOO 3500
RellItlve Wave numbers (cm·~
Fig. 3 - Rutil spectrum measured on the Salten Forest

sample.
The samples prove to be of very different composi-

tions (Fig. 1-7) with all of them presenting small
amounts of minerals which are not fitting into any of
11XlO 1SOO 2DDO 2501) 3lXlO 3500
the largely accepted Mars mineralogy models (e.g.
Quartz in fig. 4 CORO in fig 5).
Fig. 6 - Epidote spectrum measured on the Riverside
sample.
From a second batch of the same samples all the

organics were washed away using acetone and the lack
of organics was proved by GC-MS. Acetone was re-
tained in rather large amount by the powder samples.
The presence of acetone was recorded also by the Ra-
man spectra measured on the washed samples as Fig.
7 shows.
~ ,=
RelllHve WaYelllmbefli (an"')
Fig. 4 - Quartz spectrum measured on the Salten For-

est sample.
llXlO 1'OC1 2000 ;z:;oo 3lXlO 3500
Relal/ve Wavenumbers (an"~
Fig. 7 - Phylosilicate spectrum and the presence of

acetone measured on Salten Forest sample after organ-
100(1 1SOO 2lXICl 2501) lOXI 3500
ics were washed out.
RellrliYe WaVl!flumbefli (an")
Fig. 5 - Amorphous carbon (CORO) spectrum meas-

ured on the Salten Forest sample.
All off the samples gave very high fluorescence

background (excitation from 476 to 676nm) which
THE CALI METEORITE: LUMINESCENCE OF A RECENTLY FALLEN HIL ORDINARY

CHONDRITE.1. M. Trigo-Rodriguez!, 1. L1orca', and D.W.G. Sears', I Institute of Space Sciences (CSIC-IEEC).
Campus UAB, Facultat de Ciencies, Torre C5-p2. 08193 Bellaterra, Spain. ' Institut de Ti:cniques Energetiques.
Universitat Politecnica de Catalunya, Diagonal 647, ed. ETSEIB. 08028 Barcelona, Spain. 3 Arkansas Center for
Space and Planetary Sciences, University of Arkansas, Fayeneville. Arkansas 72701, USA.
Introduction: The Cali meteorite fall occurred on

6 July 2007 at 21h33m±Im UTC. In a recent paper [I]
we characterized this meteorite as a new HIL ordinary
chondrite, and also studied the circumstances of this
fall. In total, 10 meteorite samples with a total mass of
478 g were recovered around 3"24.3' , 76'30.6'W [I].
Most of the specimens found were quickly identified
as meteorites because they exhibited a prominent fu-
sion crust covering part of their surface (Fig. I). Two
astronomical associations, the Asociacion de Astrono-
mas Aficionados de Cali (ASAFI) and the Escuela de
Astronomia de Cali (EAC) participated in the recovery.
They also collected bolide reports in several munici-
palities of the Cauca Valley. Some eyewitnesses heard
audible detonations a few minutes later of seeing the
bolide. In the following minutes some meteorites pene- Fig. 1. The first recovered meteorite by J. Garcia
trated the roofs of several houses on the outskirts of was a 76.6 g piece that exhibits fusion crust over about
Cali. The interior of those pieces that broke during 40% of the samples surface. The scale in the upper left
impact appear granular and dominated by large chon- corner is 1 em.
drules. Most of the large pieces were broken, but the
small ones are completely fusion crusted. The meteor- Results and discussion: Bulk chemistry reveals
ite appears to be brecciated. that the measured abundances for most elements
The visual observations made of the daylight bo- closely match the values recorded for other ordinary
lide from several locations around the Cauca Valley chondrites classified as HIL, including Bremervorde
allowed the determination with moderate accuracy of (HIL3.9) and Tieschitz (HIL3.6) [5].
the atmospheric trajectory, radiant, and range of orbital We determined a natural TL value of34±1 krad for
elements of the progenitor meteoroid [1]. Some as- Cali, consistent with an observed fall with a "nonna'"
sumptions of the bolide preatmospheric velocity sug- radiation and thermal history [3], i.e. similar to the
gest an origin in the main asteroid belt as in the case of -95% of falls that have not been within 0.95 AU of the
the nine previous meteorites with known orbital ele- Sun (which would cause a factor of 10-100 lower natu-
ments [2]. Here we will focus in the luminescence ral TL; Hasan et aI., 1987) and have not recently
properties of the meteorite that also give infonnation (within the last 10' years) transferred to a near-Earth
on the thennal history of the progenitor meteoroid. orbit (like the major ALH 85 I 10 fall and its many
paired fragments; [3]). These results are consistent
Methods: Natural and induced thennolumines- with the orbit calculated above from eyewitness obser-
cence properties were measured in two fragments of vations.
stone #6 using apparatus and techniques described in TL can be also applied to characterize the petro-
earlier publications (e.g., [3]). The bulk composition of logic type. Induced TL properties relate to the amount
Cali was detennined on two samples from an -1.2 g and nature of the major luminescence phosphor, which
fragment of the interior of stone #6 by wet chemical in ordinary chondrites is feldspar. This, in turn, de-
methods [4]. Two independent methods were used for pends mainly on the metamorphic history and thus the
sample preparation, {l) an acid digestion treatment in a petrologic type of the meteorite. Sears et al. (1980)
sealed Teflon reactor; and (2) alkaline fusion in a zir· first showed that petrologic types 3, 4, 5 and 6 had TL
conium crucible. Analyses were performed by means sensitivity ranges of 0.002 to \.0, \.8 to 6.0, 6.0 to 14,
of inductively coupled plasma mass spectrometry and 6.0 to 25, respectively. While considerable work
(ICP-MS) and inductively coupled plasma optical has been published on the type-3 ordinary chondrites,
emission spectroscopy (ICP-OES). very little attention has been given to the higher types.
Based on existing data, our Cali induced TL meas- Conclusions: The Cali meteorite is an H/L4 ordi-
urements of 1.28 and 1.64, relative to Dhajala. suggest nary chondrite breccia as established in [I]. Bulk
that this meteorite is either a very high type 3 (say 3.8 chemistry reveals that the measured abundances for
or 3.9) or petrologic type 4. The peak temperature and most elements closely match the values recorded for
peak width, i.e. the temperature during readout at other ordinary chondrites classified as HIL. Minera-
which induced TL intensity is at a maximum and the logical and physical properties are intermediate be-
width of the peak at half-maximum, are 192±15'C and tween Hand L chondrites. The thermoluminescence
137±12 ·C, for the first sample and 178±4 ·c and value of 34 ± 1 krad is also consistent with an ob-
139±1 ·c for the second sample, which would also be served fall with a "nonnal" radiation and thennal his-
consistent with a high (greater than 3.5) petrologic tory that originated from a progenitor meteoroid that
type. has not been within 0.95 AU of the Sun and has not
Other properties indicate that Cali is petrologic recently (within the last 10' years) been transferred to
type 4 rather than high type 3. These include its mod- a near-Earth orbit. These conclusions are consistent
erate degree of recrystallization. the absence of igne- with the range of orbital elements calculated from
ous glass in most chondrules (and presence of turbid eyewitness observations.
glass in a few chondrules), the occurrence of polysyn-
thetically twinned low-Ca clinopyroxene phenocrysts
in some porphyritic pyroxene (PP) and porphyritic
olivine-pyroxene (POP) chondrules (Fig. 2), and rela-
tively homogeneous olivine and heterogeneous low-Ca
pyroxene compositions. On the other hand. the brecci-
ated nature of this meteorite is well exemplified by the
presence of fine-grained clasts all over the matrix (see
e.g. Fig. 3). Using the criteria of Van Schmus and
Wood (1967), PMD,oO for olivine is 4%, which is be-
low the 5% minimum value defined for type 3 chon-
drites. This low value. coupled with the large scatter in
pyroxene compositions (PMD FeO for low-Ca pyroxene
is 35%) is similar to observations from other type 4
chondrites (Dodd et aI., 1967), reflecting slower diffu-
sion of Fe in pyroxene than in olivine during thennal
metamorphism. Fig. 3. Transmitted optical microscope image of
detached fine-grained clasts forming part of the matrix
of this meteorite. The scale in the lower left corner is 1
mm.
References: [1] Trigo-Rodriguez J.M., et al.

(2009) Meteoritics & Planet. Sci. 44, in press.
[2] Trigo-Rodriguez J.M. et al. (2006) Meteoritics &
Planet. Sci. 41, 505-517. [3] Benoit P.H., Jull AJ.T.,
Mckeever S.W.S. and Sears D.W.G. (1993) Meteorit-
ics 28:196-203. [4] Llorca J. et al. (2007) Meteoritics
& Planet. Sci. 42:AI77-AI82. [5] Kallemeyn, G.W. et
al. (1989) Geochim. Cosmochim. Acta 53:2747-2767.
Fig. 2. Transmitted optical microscope image of a

porphiritic chondruJe of Cali meteorite. The scale in
the upper left corner is 1 mm.
PHOTOLUMINESCENCE STUDY OF HYDROGEN-RICH GRAY-TO-BLUE-TO-VIOLET DIAMONDS

FROM THE ARGYLE MI E, AUSTRALIA. C. H. van der Bogert', C. P. Smith', T. Hainschwang', and S. F.
McClure', 'lnstitut fUr Planetologie, Westfalische Wilhelms-Universitiil, Wilhelm-Klemm-Str. 10,48149 MUnster,
Germany (vanderbogert@uni-muenster.de); 'American Gemological Laboratories, New York, NY; 'Gemlab Gemo-
logical Laboratory, Balzers, Liechtenstein; 4Gemological Institute of America, Carlsbad, CA.
Background: Although a common impurity in

type Ia diamonds, hydrogen is thought to influence
the color of only a small proportion of them [1].
These relatively H-rich diamonds fall into four color
groups as described, along with their gemological,
and lR and UV-Vis spectral characteristics, by
Fritsch et al. [2,3] and Fritsch and Scarratt [1,4] as:
(I) "brown to grayish-yellow to green," (2) "white,"
(3) "chameleon," and (4) "gray to blue to violet."
Various studies have shown that the IR spectra of all
the color groups of H-rich diamonds are dominated
by H-related peaks and suggested that their UV-Vis
spectra may be influenced by the relatively high H
content [1-4; see also 5,7]. PL [5] and electron para-
magnetic resonance [6] investigations of H-rich dia-
monds with different colors have indicated that those
with gray-to-blue-to-violet colors (HGBV) contain
certain types of nickel defects that may also influence
their color.
Approach and Methods: We collected IR, UV-
Vis, and PL spectra for 20 HGBV gem-quality fac-
eted diamonds from the Argyle Mine, Australia with
a range of colors including gray-blue, grayish blue,
gray-violet, and grayish violet [7]. The goal was to
characterize HGBV diamonds with a range of colors
and investigate the relationships between the colors
and IR, UV-Vis, and PL spectral characteristics. Here
-488nm
-614nm
-633nm Figure 1. PL
spectra of a
grayish violet dia-
mond collected at
-77 K using three
different laser
excitation wave-
lengths (scaled to
the Raman peaks-
marked 'R). Many
of Ihe major PL
peaks are related
to Ni defects (see
texl).
.90 540 590 640 690 740 790 840 890 940 990
Wavelength (nm)
694 om peak (Fig. 1). There were also weaker bands minescence of the 669, 689, and 701 nm peaks.
at 659, 717, and 727 nm. The 717 and 727 nm peaks Discussinn: The 604, 659, 669, 701, 788, and 794
are phonon sidebands associated with the 701 nm om PL centers have all been attributed to i defects
vibronic system [5]. The 604 nm system, also present [5,8]; the 689 and 694 nm peaks are tentatively at-
at this excitation, was stronger in the violet-hued tributed to Ni defects [5]. Thus, the PL spectra of
stones [7]. As in the 488 nm excitation, the overall HGBV diamonds exhibit multiple peaks associated
strength of the dominant peaks was strongest in the with Ni-related defects. The greater intensity of many
stones with the most saturated violet color [7]. of the features in more violet stones indicates that Ni
633 nm excitation. A 794 (NE8) nm peak domi- defects, in addition to a high H content, play an im-
nated this excitation (Fig. 1). Additional peaks were portant role in the coloration of these diamonds [7].
present at 694, 701, 717, and 727 nm. Many of the A greater concentration of PL-active Ni defects
stones exhibited a GRI ZPL (741/744 doublet) from were also found to be associated with yellowish
natural radiation damage. At this excitation, the rela- green fluorescing areas (with more saturated violet
tionship to color grade is less clear [7]. Some stones color) than with blue fluorescing areas (with less
with more saturated violet color exhibited weak saturated color). This confirms that the yellowish
peaks at 788, 813, and 830 nm. Features at 813 and green fluorescence is associated with Ni defects, as
830 nm are associated with the ZPL at 794 om [5]. suggested by [5,6].
488 nm excitation spot analyses. We also inves-
tigated the differences between the yellowish green References: [I] Fritsch and Scarratt (1992) Gems &
and blue fluorescing regions seen with a Diamond- Gemology 28, 35-42. [2] Fritsch er al. (1991) Mal. Res.
View deep ultraviolet microscope (Fig 2, inset). We Soc. Int. Can! Proc. 671-676. [3] Fritsch et al. (2007) New
collected PL spectra from three focused areas: yel- Diam. Front. Carbon Tech. 17,63-89. [4] Fritsch and Scar-
lowish green, weak-to-moderate blue, and strong ratt (1993) J. Gemmology 23, 451-460. [5] 1akoubovskii
blue fluorescing spots (Fig 2, inset) using a 488 nm and Adriaenssens (2002) Diam. Rei. Mal II, 125-131. [6]
excitation wavelength. The strong blue spot corre- Noble et al. (1998) J. Physics: Condo Mal. 10, 11781-
sponded to a region of less saturated color in the
11793. [7] van der Bogert et al. (in press) Gems & Gemol·
sample, while the yellowish green and weak-to- ogy 45. [8] Bokii er al. (1986) Natural and Synthetic Dia-
moderate blue fluorescing areas correlated to the
monds, Moscow, 31 p.
more saturated violet color. The yellowish green spot
Acknowledgemems: The data for this study were col-
exhibited the strongest photoluminescence: 669,689,
lected when all the authors were employees of the Gemo-
and 701 nm peaks, and 659 and 717 nm peaks. The
logical Institute of America.
604 nm series was also present. The spectra from the
blue-fluorescing regions had much lower overall lu-
_Grnn Spot.'
-BlueSpat.2 Figure 2. Focused
-Blight Blue 5p01.]
PL spectra (488
nm excitation,
scaled 10 the Ra-
man peak al 521
nm) for three SpOIS
on a grayish violet
diamond that had
differing fluores-
cence colors in the
deep ultraviolet
(see inset). The
yellowish green
areas had stronger
Ni-related PL
peaks than the
blue areas.
475 5tltl 525 550 575 500 525 650 675 700 725 750 no 800
Wavelength (nm)
PATHWAYS AND RATES OF Mg-SULFATE DEHYDRATION AND REHYDRATION ON MARS.

Alian Wang, John J. Freemen, Dept Earth and Planetary Sciences and McDonnell Center for Space Sciences, Wash-
ington University, St. Louis, MO, 63130 USA (alianw@levee.wustl.edu)
We report a new understanding developed on the In the -I O·C ,; T ,; 50·C range, the stability fields of
basis of experimental study [1,2,3] of the hydrous Mg- LH-l w, MH-I w, 4w, and Am are partially overlap in
sulfates, using humidity buffer technology and non- low-mid RH range (Fig. I).
invasive Raman spectroscopy. Rate of dehydration and rehydration: Rate infor-
Stability field and phase transition pathways: mation was extracted from Raman ill of intennediate
Infonnation came from direct Raman phase identifica- reaction products measured at regular time interval
tions and gravimetric measurements (Fig. I): during the dehydration/rehydration experiments. Most
At T<50·C, hexahydrate (MgSO"6H,O,6w), ep- experiments (except vacuum desiccation for amorphi-
somite (MgS0 4·7H 20,7w), and meridianiite zation [4]) were conducted under terrestrial P H2 0 (with
(MgSO.-J 1H,O, II w) precipitate from Mg-S-solution. selected RHs) which would increase the general rate of
Kieserite (MgSO,'H,O, 1w) only precipitates from high reaction. Therefore, only the ratio of rates at different
temperature (T) aqueous solution (95°C in our experi- temperatures is meaningful for their applications to
ments). Mars. Sources of errors affecting the rate estimations
At T<50·C, starkeyite (MgSO..4H,O,4w) (not kie- are (l) the limited number of experiment temperatures
serite) is the dehydration end product from 11 w, 7w, (three) used for rate extraction and (2) the limited
6w. Amorphous Mg-sulfates (Am) form by fast dehy- number of intennediate stages when Raman ID was
dration of Ilw, 7w, 6w (not from 4w or Iw), and it made on the reaction products. For these reasons, we
can hold a maximum 3 water per 804 . use only the order of magnitude of rate ratios in the
At T< 50·C, kieserite is only formed through two discussions to judge whether a process has the poten-
pathways from the dehydration of6w, 7w, llw; (1) if tial to happen on Mars.
these salts were originally mixed with Ca- and Fe- The rate of amorphization is strongly controlled by
sulfates, Fe-hydroxide and Fe-oxide; or (2) the salts temperature [4]. The amorphization process matches a
were first converted to amorphous phases. first-order forward reaction whose rate can be esti-
We found that MgSO,'H,O has two polymorphs, mated by k(T)~ln2ltn(T). The rate k at 21 ·C is - 120
LH-lw and MH-Iw (kieserite). The LH-lw forms times the k at -8 ·C in our experiments. When extrapo-
from the dehydration of 6w, 7w, Ilw by above two lating into 210-240 K range (4 to 8 o'clock at Spirit
pathways. The MH-I w precipitates from high T aque- site [5,6,7] while RH drops from 10% to -0%), the rate
ous solution, and can also be formed from the conver- of amorphization would be 10" to 10-7 of that at 21 "C.
sion ofLH-1 w at mid-range relative humidity (RH). The dehydration and rehydration processes of most
We found that MgSO,'7H,O has two polymorphs, Mg-sulfates match roughly the first-order forward re-
7w (epsomite) and LT-7w. LT-7w is stable at T ,; - action within the errors stated above.
10·C. Fig. 1 shows the phase boundary between II w The rate of 7w dehydration at 21·C is - 50 times the
and LT-7w. The extent of the stability fields ofLT-7w rate at 5°C, in our experiments for total conversion to
and II w below -10 ·C has not been undetermined yet. 4w at II %RH (Earth P H2o). Extrapolating to 240K
Above 0 ·C, the rehydration pathways of LH-I w, would decrease the rate of dehydration - 5000 times.
4w, Am are different. Amorphous phase rehydrates to In 240K - 290K daytime ground temperature at Spirit
4w first, then to 6wl7w, while LH-I w rehydrates to 6w site [5,6,7], this dehydration can proceed steadily.
without go through 4w. 4w rehydrates to 6wl7w. Using the same method (experimental data plus ex-
Am lw 1w+6w 4w 6w 7w LT-7W llW deli trapolation), we found that the rehydration rates of Iw,
• • • • • • • • •
80
4w, and Am would be very low in temperature range
180K-210K (0 to 4 o'clock at Spirit site [5,6,7] while
Fig. 1 Stability fields RH increases from 10% to 100%). For example (Fig.
60 2), the rehydration rate of Am (to 4w, 6w, 7w) at 180
~ K for 100% RH and for 35% RH would be 5x10" and
e .. 10" times of that at 21·C. At Earth P H2o, that means >5
~
7w·deiq
years at 100%RH and > 83000 years at 35%RH, and
•
••
-.00
Q.
E 20 hundreds times more at Mars PH2o.
•
l- Application to Mg-sulfates on Mars: Based on the
0 •• information of pathways and reaction rates from ours
and other experiments [8], we developed the following
eo
hypotheses (Fig. 3).
-20
Relative Humidity (%)
90 LP! Contribution No. 1473
Precipitation - 7w would be the major Mg-sulfate the critical condition to fonn amorphous Mg-sulfates is
phase precipitated from Mg-S aqueous solutions on to rapidly extract H 20 from 7w/6w causing structural
Mars, because the surface temperature in Mars' gen- collapse. This condition can not be satisfied if the reac-
eral area was never above 50°C, even in its wann and tion rate is too low. In addition, because of the low rate
wet past. During a localized hydrothermal event, MH- .of 1wand 4w rehydration at low T, not much 7w can
1w (kieserite) would precipitate from aqueous solu- be formed during diurnal cycles, while Am can only be
tion. For low temperature Mg-S aqueous solutions (2 formed from II w, 7w, or 6w, but not from 4w or Iw.
°C ::;; T ::;; -3 DC, the freezing point suppression by satu- Conclusion: Our hypothesis developed based on a
rated MgSO. is only -3 'c), 11w would precipitate. set of experiments referred to in this abstract indicates
Dehydration - With Mars getting colder and drier, 7w that Iw, 4w, and llw should be the current sta-
and 11 w (if they do not coexist with water ice) would ble/metastable Mg-sulfates on Mars.
start to dehydrate. The kinetic barrier at <50'C would
prevent the direct dehydration of 7wIJ Iw to Iw. The Acknowledgement: This study was fund by a Mars Fun-
dehydration would stop at starkeyite (4w). damental Research project (NNX07AQ34G).
At the locations where the chemistry of original References: [I) Wang et al (2006), GCA. 70.6118-6135.
brine allowed the co-precipitation of Ca-sulfates, Fe- [2) Wang et aI. (2008), JGR, 114. JE003266. [3) Freeman et
sulfates, and Fe- hydroxides, or the processes built up a1 (2009), this volume. [4J Wang et a1 (2007), 38'" LPSC.
the mixture ofMg-sulfates with other minerals (includ- # 1196. [5]Smith et al (2004), Science. 306, 1750- I 752.
ing Fe-oxides), the coexisting species would function [6) Spanovich et al (2006), Icarus. 180. 314-320. [7) Smith
as a catalyst in the dehydration of 7w/ll w, overcom- et al (2006), JGR. Ill, E12S13. [8)Chipera et al. (2007),
ing the kinetic barrier to reach LH-I w as the final de- GCA, 71,241-250.
hydration product. Rapid dehydration of 7w/ll w dur- Figure 2. Rehydration of Pm to 4w or 6w or 7w
ing the early stage (when temperature on Mars was not
very low) would form amorphous Mg-sulfates. How- • data@l:31-34%RH 1:1 data@74-76%RH
• data@1000/oRH I:J. extrap@31.34%RH
ever, the gradual decreasing of PH20 in Mars atmos- D. ~rap:'@74-7SY~~~._. _. _ I:J. ~rap:@10()<V~RH __ . _. _
phere can cause the continuation of Am dehydration, R2

::: 0.9802
thus to form LH-I w. 6
In mid-low obliquity period like current Mars, the
MH-I w (precipitated from hydrothermal aqueous solu-
tion), LH-Iw and 4w (formed from the dehydration of
7wIJ 1w) would be stable/metastable over most of
Mars. The II w could occur and be stable near the Po- 6-
lar Regions where it might co-exist with water ice. ~= 0.9955
Rehydration - In high obliquity period on Mars, water

ice would fonn at low altitude regions. The coexisting
water ice (I OO%RH) will stimulate the rehydration of
Iw and 4w. Because the low obliquity period can last
for millions of years, the rehydration can progress
-125 -100 -75 -so ·25 0 25 so 75
Temperature Ie)
steadily even at extremely low rates to form 7w (LT-
7w). The 7w would gradually convert to Ilw.
During the diurnal cycle - During a diurnal cycle on Mg. S-brine
(hydrothermal)
Mars, the high RH(s) that can induce the rehydration
of Iw, 4w, Am would last only a few hours in the early >342 K
morning on Mars (i.e. 1-2 hrs at 100% RH and <4 hrs :;0
:r:
at > 10% RH derived from T measurements at rvrnR Co
"''""
sits [5, 6, 7]). In addition, this period would be imme-
~
diately followed by a >20 hrs dehydration period at
Il>
RH of -0%. Therefore we believe that it is almost im-
possible for these rehydrations to occur and to proceed "''"
during a diurnal cycle on Mars.
Similarly, the probability of forming amorphous
Mg-sulfates during a diurnal cycle is also extremely
low, because of the very low rate of amorphization
(from the 6w17w phases) at this low temperature
(21OK-240K while RH drops from 10% to -0%). Note Figure 3. Pathways of forming martian Mg·sulfates
BEHAVIOVR OF VITROCERAMICS FOR NUCLEAR WASTE STORAGE PROBED BY RAMAN

AND LUMINESCENCE
Gerard Panczer, Clement Mendoza, Dominique de Ligny., Laboratoire de Physico-chimie des Materiaux
Luminescents, VMR 5620 CNRS, Vniversit" Lyon 1,69622 Villeurbanne, France
In France, the fissions products and the of their structural local environment were followed
minor actinides product by the nuclear industry are by luminescence spectroscopy. The environment of
vitrified. In the near future it is planed that for each the REE and the irradiation induced defects could
waste solution will correspond a specific glass be analysed by photoluminescence in natural phases
matrix. The SUM02-l2c glass (Vmo) is the specific and synthetic ones thanks to the three luminescent
Mo-rich borosilicate matrix developed to store centers : MoO, groups, Nd'+ (figure 2) and Eu'+
Umo-MoSnAI solution residues. During its cooling, used as structural probes.
this glass becomes polyphased and some
crystallized and amorphous phases appear. The ,0‫סס‬oo
Lumlnesoenoe spectra
main crystalline phase is the calcium molybdate 0‫סס‬oo >.- 53:2.5 rwn
CaMo0 4 , powellite. The preferential incorporation - Md" Ooped pQ\l'eIIi\f aystaI
of the fissions products (FP) and the minor ""'" - Md" doped SNCM glaM
-Md" eloped ~ glau
Nd3+
,‫סס‬OO
actinides (MA) in the powellite must be understood 4F1rl~41g!2
as well as the effect of self irradiation (swelling, !d ""'"
microcracks... ). Therefore Eu, Nd and Pr rare earth j 0‫סס‬oo
elements (REEs) were used as FP and MA

surrogate. "'"
0‫סס‬oo
20000
The formation of the powellite in the glass
,‫סס‬oo
and its structural modifications were followed by 800 850 nm 900 e50
Raman spectroscopy (Fig.]). Wavele1lQth (nm)
Figure 2: Nd luminescence spectra of the
~man apectra different phases of the Mo rich borosilicate
""'" l . _ : $32.5 nm
vl vitroceramic
-SNCMpu
'. 6
""'" -OSNC_
-~~cryat8I
<0'00 ?~., For a better understanding of the powellite

physical properties, natural and synthetic crystals
b
.~ 30000 were studied as welL Some of the natural samples
:;; were selected because they overcome natural self
v2 Vitroceram
20000 v4 irradiation (V and Th content).
Crystal
The major points are the crystals
morphology changes drastically with its thermal
500 Crrr1 1000 history and that REEs are preferentially
Raman shift (em"') concentrated in the powellite crystals. Synthetic
Figure ]: Raman spectra of the different samples and the vitroceramic will be implanted hy
phases of the Mo rich borosilicate vitroceramic heavy ion beam simulating self irradiation alpha
damages.
The incorporation of the REEs by the
crystalline structure CaMo04 and the modifications

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Program and Abstract Volume

Local Organizing Committee

LPI Contribution No. 1473

Abstracts in this volume may be cited as

This volume is distributed by

ISSN No. 016 I-5297

Application of Cathodoluminescence to Recognize Diagenetic Trends of Carbonate Rocks

Ca-poor Pyroxine Raman Characteristics in H Ordinary Chondrites

Micro-Raman Determination of the Composition ofUgrandite Garnets

Raman Spectra of a Fine-grained Labradorite Sample Heated to Typical

Characterization hy Cathodoluminescence Spectroscopy of Silica Phases as Indicator of the

Spectrally-resolved Thermoluminescence on Hydrothennal Aragonite

LuCIDD: A Luminescence Instrument with Confocal and Imaging Units for

ODIN: A Prototype Miniature Luminescence Instrument for Dating of Martian Regolith

Confocal Raman Imaging in Geosciences

Impulse Cathodoluminescence Silicate Glasses

Investigating the Oldest Traces of Life by AFMlConfocal Raman Spectroscopy:

Gated Laser-based Spectroscopy of Minerals: Luminescence, Raman, LIBS

Spectrally-resolved Luminescence of Moganite from Mogan (Gran Canaria)

Cathodoluminescence of Lunar Minerals and Rocks

Cathodoluminescence Microscopy and Spectroscopy of Shocked Zircon from the

Scanning Electron Microscope-Cathodoluminescence and Micro-Raman Properties of

Cathodoluminescence Characterization ofNanodiamonds: An Application to the

Thermo-Luminescence Glow Curves and Photoluminescence afton Irradiated AhO)

Cathodoluminescence and Raman Spectroscopic Characterization of Experimentally

Cathodoluminescence Characterization of Maskelynite and Alkali Feldspar in Shergottite

MoonShot: A Combined RamanlLffiS Instrument fnr Lunar Exploration

CL Study of the Low-Grade Feldspar Alteration

Decoding Environmental Conditions During Silicification of Plant Stems in Equatorial Pangaea

Cathodoluminescent Features and Raman Spectroscopy of Miocene Hydrothennal

Evidence of Shock Metamorphism in Hungarian L-Chondrites Using Raman Spectroscopy

Thennoluminescence Study of Ordinary Chondrites

Cathodoluminescence Microcharacterization of Ballen Silica in Impactites

Spectral and Microscopic Analyses of Fossil Microorganisms in a Jurassic Oolitic Limestone

In-Situ Micro·Raman and Moessbauer Spectroscopic Study of Evaporate Minerals in

Mineral Characterization of Silicified Coral from \Vestem Sumatra, Indonesia

Cathodoluminescence (CL) Studies ofUHP-Metamorphic Rocks from Dora MairalWestem Alps:

Order-Disorder in K-Feldspar Grown from Mixed Magmas - CL and Raman Study

Micro-Raman Spectroscopy ofNWA 4047 Meteorite

Comparative Raman Study of Different Mars Analog Materials

The Cali Meteorite: Luminescence of a Recently Fallen HIL Ordinary Chondrite

Photoluminescence Study of Hydrogen-rich Gray-to-Blue-to-Violet Diamonds from the

Pathways and Rates ofMg-Sulfate Dehydration and Rehydration on Mars

8:45 a.m. Gucsik A.·

9:00 a.m. Gaf! M. * [INVITED]

9:45 a.m. BREAK

MICRO-RAMAN STUDIES OF TERRESTRIAL MATERIALS

Chairs: Michael Galt

10:10 a.m. Tareea N. * Hilchenbaeh M. Goetz W. Steininger H. Popp J.

10:30 a.m. Bersani D. * Andil S. Vignola P. Marino I.-G. Lottiei P. P.

10:50 a.m. Korsakov A. V. * Dieing T. Golovin A. V. Toporski J.

11: 10 a.m. Dieing T. * Jauss A. Schmidt U. Toporski J.

II :30 a.m. Panezer G. * Mendoza C. de Ligny D.

11 :50 a.m. LUNCH

Thursday, April 2, 2009

Chairs: Alian Wang

I:30 p.m. Foucher F.' Westall F.

2:10 p.m. Karczemska A.' Jakubowski T. Kozanecki M. Szurgot M. Gucsik A. Mirura S.

2:30 p.m. Wang A.' Freeman J. J.

2:50 p.m. BREAK

Thursday, April 2, 2009

Chairs: Suporn Boonsue

3:30 p.m. Kayama M.· Gucsik A. Nishido H. Ninagawa K. Tsuchiyama A.

3:50 p.m. Boonsue S.· Spray J.